CN108503672B - 锇过氧配合物及其制备方法和应用 - Google Patents
锇过氧配合物及其制备方法和应用 Download PDFInfo
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- CN108503672B CN108503672B CN201710973435.8A CN201710973435A CN108503672B CN 108503672 B CN108503672 B CN 108503672B CN 201710973435 A CN201710973435 A CN 201710973435A CN 108503672 B CN108503672 B CN 108503672B
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- oxygen
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- -1 Osmium peroxide Chemical class 0.000 title claims abstract description 92
- 229910052762 osmium Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000010668 complexation reaction Methods 0.000 title description 2
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 42
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000001301 oxygen Substances 0.000 claims abstract description 40
- 150000001298 alcohols Chemical class 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 38
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 36
- 238000007254 oxidation reaction Methods 0.000 claims description 32
- 230000003647 oxidation Effects 0.000 claims description 30
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 20
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 18
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 18
- 125000001424 substituent group Chemical group 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000012434 nucleophilic reagent Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 6
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 4
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 claims description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 4
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 claims description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 3
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 3
- 229940116357 potassium thiocyanate Drugs 0.000 claims description 3
- ZGJADVGJIVEEGF-UHFFFAOYSA-M potassium;phenoxide Chemical compound [K+].[O-]C1=CC=CC=C1 ZGJADVGJIVEEGF-UHFFFAOYSA-M 0.000 claims description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 3
- RZWQDAUIUBVCDD-UHFFFAOYSA-M sodium;benzenethiolate Chemical compound [Na+].[S-]C1=CC=CC=C1 RZWQDAUIUBVCDD-UHFFFAOYSA-M 0.000 claims description 3
- MGAXYKDBRBNWKT-UHFFFAOYSA-N (5-oxooxolan-2-yl)methyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCC1OC(=O)CC1 MGAXYKDBRBNWKT-UHFFFAOYSA-N 0.000 claims description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 2
- MHFGGKKVDZSTKK-UHFFFAOYSA-N 4-methylphenol;sodium Chemical compound [Na].CC1=CC=C(O)C=C1 MHFGGKKVDZSTKK-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 150000007529 inorganic bases Chemical class 0.000 claims description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 2
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- FSBUHBOKPUXFKL-UHFFFAOYSA-M sodium;4-methoxybenzenethiolate Chemical compound [Na+].COC1=CC=C([S-])C=C1 FSBUHBOKPUXFKL-UHFFFAOYSA-M 0.000 claims description 2
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 abstract description 10
- 239000000758 substrate Substances 0.000 abstract description 9
- 150000001728 carbonyl compounds Chemical class 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 52
- 238000006243 chemical reaction Methods 0.000 description 42
- 239000003446 ligand Substances 0.000 description 37
- 239000012295 chemical reaction liquid Substances 0.000 description 36
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 28
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 20
- 238000005160 1H NMR spectroscopy Methods 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 14
- 239000003480 eluent Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000001816 cooling Methods 0.000 description 12
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 12
- 239000003208 petroleum Substances 0.000 description 12
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 12
- 239000000741 silica gel Substances 0.000 description 12
- 229910002027 silica gel Inorganic materials 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- 229910001882 dioxygen Inorganic materials 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical group CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 5
- 125000002252 acyl group Chemical group 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 5
- 150000001719 carbohydrate derivatives Chemical group 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 125000004185 ester group Chemical group 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 150000002825 nitriles Chemical class 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical group [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 4
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 4
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 3
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 3
- 238000004679 31P NMR spectroscopy Methods 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 description 3
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 3
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 229920002674 hyaluronan Polymers 0.000 description 3
- 229960003160 hyaluronic acid Drugs 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XGCDBGRZEKYHNV-UHFFFAOYSA-N 1,1-bis(diphenylphosphino)methane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CP(C=1C=CC=CC=1)C1=CC=CC=C1 XGCDBGRZEKYHNV-UHFFFAOYSA-N 0.000 description 2
- 238000004701 1H-13C HSQC Methods 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- AEMOLEFTQBMNLQ-WAXACMCWSA-N alpha-D-glucuronic acid Chemical compound O[C@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O AEMOLEFTQBMNLQ-WAXACMCWSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
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Abstract
Description
技术领域
本发明涉及金属有机化学、小分子活化和催化领域,具体地,涉及锇过氧配合物及其制备方法和应用。
背景技术
金属有机化学是研究金属有机化合物的合成、结构、反应、性能及应用的一门前沿学科。其与医药合成、能源材料、环境生命息息相关,成为近代化学前沿领域之一。随着金属有机化学的发展,金属配合物广泛的应用于有机催化反应,对合成化学的发展起到重要的推动作用。
醛酮等羰基化合物,因具有活泼的羰基官能团,容易进一步衍生化得到新的一类化合物,所以常被用作医药合成或化工生产中重要的原料。在农药、染料、化妆品以及添加剂等行业中占有非常重要的地位。目前,大部分醛酮化合物是由醇经选择性氧化而得到。因此,高选择性的氧化醇得到相应的羰基化合物,无论是在基础有机合成,还是在工业生产中都具有重要意义。对于醇的氧化反应,传统的方法为计量氧化,即采用铬锰试剂、高价碘试剂、Jones试剂等强氧化剂实现醇到羰基化合物的转化。虽然这些方法转化效率较高,但很容易深度氧化成相应的羧酸,并且成本高,伴随产生大量废弃物,造成环境污染。
分子氧(O2)具有丰富、廉价以及其副产物为环境友好的H2O和/或H2O2等优点,一直以来被视为十分理想的氧化剂。但是基态的分子氧表现出化学惰性,不能直接将底物分子氧化,需要借助催化剂将分子氧活化后,才能在温和条件下将有机底物氧化。考虑到经济和环境的因素,人们更倾向于采用分子氧作为氧化剂,过度金属催化醇氧化。近年来,尽管在这方面取得了一定的进展,但这些方法仍存在以下缺点:操作复杂,条件苛刻,部分需要较高氧气压;选择性差,产物不单一;底物普适性窄,如对含氮、氧、硫等杂环的醇或含大位阻基团的醇氧化效率低。
因此,开发出一种新型、高效、高选择性,反应条件温和以及具有较宽的底物普适性的催化体系取代传统的化学计量氧化方法仍是关键的一步。
发明内容
本发明的目的是为了解决传统的方法用于醇氧化存在成本高、选择性差、造成环境污染等缺陷,以及现阶段分子氧催化氧化体系存在选择性差,底物普适性窄等缺点,本发明提供了一种锇过氧配合物及其制备方法和应用。以本发明提供的锇过氧配合物为催化剂,氧气为氧化剂,应用于氧化一系列醇制备羰基化合物时,具有高选择性、较宽的底物普适性以及条件温和等优点。
本发明的发明人经研究发现,以锇过氧配合物为催化剂,以分子氧作为氧化剂,用于醇氧化时,随着醇所带取代基共轭程度的增大,越有利于醇被氧化,并且带吸电子取代基的醇比带给电子取代基的醇更容易被氧化,这与已报到的醇氧化结果截然不同,意味着该转化过程经历了不同的催化路径;同时,补充了已报到方法的不足;并且本发明对氧化含有杂原子(N,O,S)取代基的醇也具有很到的效率,从而完成了本发明。
根据本发明的第一个方面,本发明提供了一种锇过氧配合物,该配合物具有如下式(I)或式(II)中的任意一个所示的结构:
其中,
[Os]为OsL2;
L为膦配体、CO配体、吡啶类配体、氮杂环卡宾配体、腈类配体和异氰类双电子配体中的任意一种;
M-为Cl-、BF4 -、PF6 -和BPh4 -中的任意一种;
R1为位于式(I)或式(II)上标有数字1的位置上的取代基,其选自H、SCN、CN、取代或未取代的苯酚基或苯硫酚基、碳原子数为1-10的烷基、烷氧基或烷硫基等具有亲核性基团中的任意一种。
R2 +为位于式(I)上标有数字2-6的位置中的任意一个上的阳离子取代基,且R2 +为碳原子为3-27的季鏻阳离子或碳原子为4-24的季铵阳离子;
R3为位于式(I)或式(II)上标有数字2-6的位置中不同于R2 +所在位置的至少一个上的取代基;并且,R3选自H、卤素、SCN、CN、取代或未取代的芳基、碳原子为1-10的烷基、烷氧基、酰基、酯基、胺基和碳原子为2-10的烯基、炔基和能增强水溶性的取代基中的任意一种。
根据本发明的第二个方面,本发明提供了上述锇过氧配合物的制备方法,该方法包括:
使用式(III)所示的配合物与亲核试剂在氧气存在的条件下反应制备式(I)所示的配合物;
使用式(IV)所示的配合物与亲核试剂在氧气存在的条件下反应制备式(II)所示的配合物,或者通过将式(I)所示的配合物在强碱的水溶液中水解来制备式(II)所示的配合物;
其中,
所述碱可以为碱金属的氢氧化物。例如可以为NaOH和/或KOH。所述碱的水溶液的浓度可以为0.01-10摩尔/升,优选0.5-5摩尔/升。
所述亲核试剂可以为碳原子为1-10的醇钠、醇钾、硫醇钠、硫醇钾、酚、酚钠和酚钾,或氰化钾、氰化钠、硫氰化钾、硫氢化钠中的至少一种。优选地,所述亲核试剂为甲醇钠、乙醇钠、氰化钾、苯酚钠、对甲苯酚钠、苯硫酚钠、对甲苯硫酚钠和对甲氧基苯硫酚钠中的至少一种;
其中,M-、R2 +、[Os]以及式(III)和式(IV)R3与上述所述的M-、R2 +、[Os]以及R3相同。
根据本发明的第三个方面,本发明提供了上述锇过氧配合物在催化醇氧化反应中的应用。
本发明提供的锇过氧配合物具有高的热、空气、水和光照稳定性以及制备过程简单等特点。当将其用于催化醇氧化反应是,表现出高选择性,宽的底物普适性。
本发明的其他特征和优点在随后的具体实施方式部分予以详细说明。
附图说明
附图是用来提供对本发明的进一步理解,并且构成说明书的一部分,与下面的具体实施方式一起用于解释本发明,但并不构成对本发明的限制。
在附图中:
图1为本发明制备例2制备得到的式(II-1)所示的锇过氧配合物的高分辨质谱图;
图2为本发明制备例2制备得到的式(II-1)所示的锇过氧配合物的X-射线衍射晶体结构图。
具体实施方式
以下对本发明的具体实施方式进行详细说明。应当理解的是,此处所描述的具体实施方式仅用于说明和解释本发明,并不用于限制本发明。
在本发明中,术语“化合物”由两种或两种以上的元素组成的纯净物(区别于单质)。化合物具有一定的特性,既不同于它所含的元素或离子,亦不同于其他化合物,通常还具有一定的组成。
在本发明中,术语“配合物”为一类具有特征化学结构的化合物,由中心原子(或离子,统称中心原子)和围绕它的分子或离子(称为配位体/配体)完全或部分通过配位键结合而形成。包含由中心原子或离子与几个配体分子或离子以配位键相结合而形成的复杂分子或离子,通常称为配位单元。凡是含有配位单元的化合物都称作配位化合物。
根据本发明的第一个方面,本发明提供了一种锇过氧配合物,该配合物具有如下式(I)或式(II)中的任意一个所示的结构:
其中,
[Os]为OsL2;
L可以为但不限于膦配体、CO配体、吡啶类配体、氮杂环卡宾(N-HeterocyclicCarbenes,NHC)配体、腈类配体和异氰类双电子配体中的任意一种。
其中,所述膦配体可以为碳原子为3-24的烷基膦、环烷基膦和芳基膦;优选地,所述膦配体为三甲基膦、三乙基膦、三丙基膦、三异丙基膦、三叔丁基膦、三环己基膦和三苯基膦中的任意一种。
其中,所述吡啶类配体可以为含有吡啶或联吡啶结构单元的化合物;优选地,所述吡啶类配体为甲基吡啶、乙基吡啶、1,4-联吡啶、1,2-二(4-吡啶基)乙烯、乙烯基吡啶、乙炔基吡啶、吡啶硼酸、氨基吡啶、氰基吡啶、巯基吡啶、二甲胺基吡啶、苯基吡啶和1,2-双(4-吡啶基)乙烷中的任意一种。
其中,所述氮杂环卡宾配体可以为任何含有氮杂环卡宾结构单元的化合物;优选地,所述氮杂环卡宾配体为咪唑型氮杂环卡宾、咪唑啉型氮杂环卡宾、噻唑型氮杂环卡宾和三唑型氮杂环卡宾中的任意一种。
其中,所述腈类配体可以为含有腈基结构单元的化合物;优选地,所述腈类配体为乙腈、丙腈和苯腈中的任意一种。
其中,所述异氰类双电子配体可以为含有异氰基结构单元的化合物;优选地,所述异氰类双电子配体为环己基异氰、叔丁基异氰和苯基异氰中的任意一种。
L2可视为一个整体;优选地,L2为选自双齿氮配体、双齿膦配体、双齿碳-氮配体和双齿氧-氮配体中的任意一种。其中,所述双齿氮配体是指以双齿氮原子作为配位原子的配体,例如可以为乙二胺、2,2'-联吡啶和1,10-菲罗啉中的任意一种。其中,所述双齿膦配体是指以双齿磷原子作为配位原子的配体,例如可以为DPPM(Bis-(diphenylphosphino)methane,双二苯基膦甲烷)、DPPE(1,2-Bis(diphenylphosphino)ethane,1,2-双(二苯基膦)乙烷)和DPPP(1,3-Bis(diphenylphosphino)propane,1,3-双(二苯基膦)丙烷)中的任意一种。其中,所述双齿碳-氮配体是指以双齿碳-氮原子作为配位原子的配体,例如可以为邻苯基吡啶。其中,所述双齿氧-氮配体是指以双齿氧-氮原子作为配位原子的配体,例如可以为8-羟基喹啉。
M-可以为Cl-、BF4 -、PF6 -和BPh4 -中的任意一种。
R1为位于式(I)或式(II)上标有数字1的位置上的取代基,其选自H、卤素、SCN、CN、取代或未取代的苯酚基或苯硫酚基,碳原子为1-10的烷基、烷氧基或烷硫基中的任意一种。
R2 +为位于式(I)上标有数字2-6的位置中的任意一个上的阳离子取代基,且R2 +为碳原子为3-27的季鏻阳离子或碳原子为4-24的季铵阳离子。优选地,R2 +为位于式(I)上标有数字2-3的位置中的任意一个上的阳离子取代基,更优选地,R2 +为位于式(I)上标有数字2的位置上的阳离子取代基。
所述季鏻阳离子可以为碳原子为3-27的烷基季膦、环烷基季膦和芳基季膦阳离子中的任意一种。优选地,所述季鏻阳离子为三甲基膦、三乙基膦、三丙基膦、三异丙基膦、三叔丁基膦、三环己基膦和三苯基膦阳离子中的任意一种。所述季铵阳离子为NH4 +中的四个H分别被烃基取代后形成的阳离子。优选地,所述季铵阳离子为四甲基铵、四乙基铵、三甲基一乙基胺、四丙基铵、四异丙基铵和四叔丁基铵阳离子中的任意一种。
R3为位于式(I)或式(II)上标有数字2-6的位置,优选标有数字3-5的位置中的至少一个,更优选标有数字5的位置,且不同于R2 +所在位置上的取代基。
并且,R3可以选自H、卤素、SCN、CN、取代或未取代的芳基、碳原子为1-10的烷基、烷氧基、酰基、酯基、胺基、碳原子为2-10的烯基、炔基和能增强水溶性的取代基中的任意一种。
其中,所述卤素可以为F、Cl、Br或I。
其中,所述芳基可以为苯基、萘基、蒽基、菲基、芘基、噻吩基、呋喃基、吡啶基和吡咯基中的任意一种。
其中,所述芳基的取代基可以为碳原子为1-10的烃基、烷氧基、酰基、酯基、胺基、硝基、氰基和卤素中的任意一种。
其中,所述碳原子为1-10的烃基、烷氧基、酰基、酯基、胺基可以为甲基、乙基、丙基、正辛基、乙烯基、乙炔基、甲氧基、乙氧基、正辛氧基、乙酰基、正丁酰基、甲酯基、乙酯基、甲胺基和乙胺基中的任意一种。
其中,所述碳原子为1-10的烷基、烷氧基、酰基、酯基、胺基可以为甲基、乙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、新戊基、仲戊基、叔戊基、正己基、异己基、新己基、仲己基、叔己基、正庚基、异庚基、新庚基、仲庚基、叔庚基、正辛基、异辛基、新辛基、仲辛基、叔辛基、甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基、叔丁氧基、正戊氧基、异戊氧基、新戊氧基、仲戊氧基、叔戊氧基、正己氧基、异己氧基、新己氧基、仲己氧基、叔己氧基、正庚氧基、异庚氧基、新庚氧基、仲庚氧基、叔庚氧基、正辛氧基、异辛氧基、新辛氧基、仲辛氧基、叔辛氧基、甲酰基、乙酰基、甲酯基、乙酯基、叔丁酯基、甲胺基和乙胺基中的任意一种。
其中,所述碳原子为2-10的烯基、炔基可以为乙烯基、乙炔基、丙炔基和丁炔基中的任意一种。
所述能增强水溶性的取代基可以为聚乙二醇残基、透明质酸残基和糖类衍生物残基中的任意一种。所述聚乙二醇残基是指聚乙二醇的其中一个末端上的羟基去掉H后的部分。所述透明质酸残基是指透明质酸的D-葡萄糖醛酸或N-乙酰葡糖胺的任意一个羟基去掉H后的部分,或透明质酸的D-葡萄糖醛酸的羧基去掉OH后的部分。所述糖类衍生物残基是指糖类衍生物的任意一个羟基去掉H后的部分。所述聚乙二醇的数均分子量可以为200-200000。所述透明质酸的数均分子量可以为2000-2000000。所述糖类衍生物可以为葡萄糖、蔗糖、麦芽糖、半乳糖、乳糖、果糖和唾液酸的衍生物中的任意一种。所述糖类衍生物例如可以为葡萄糖醛酸、葡萄糖缩醛、葡萄糖半缩醛和羧甲基乳糖中的任意一种。
需要说明的是,在本发明中,取代基R2 +和R3均可以为一个或多个;如果为多个,同一个分子上的多个R2 +和R3各自可以相同或不同,只要在上述范围内即可。
根据本发明的第一个方面,优选地,所述锇过氧配合物为下列配合物中的任意一种:
以上配合物中,[Os]′和[Os]各自为Os(PPh3)2,M1 ˉ为Clˉ或BPh4 ˉ,且X为O或S。
根据本发明的第二个方面,本发明提供了上述锇过氧配合物的制备方法,该方法包括:
使用式(III)所示的配合物与亲核试剂在氧气存在的条件下反应制备式(I)所示的配合物。
使用式(IV)所示的配合物与亲核试剂在氧气存在的条件下反应制备式(II)所示的配合物,或者通过将式(I)所示的配合物在强碱的水溶液中水解来制备式(II)所示的配合物;
其中,M-、R2 +、[Os]以及式(III)和式(IV)R3与上述所述的M-、R2 +、[Os]以及R3相同。
根据本发明所述的方法,所述反应可以在有机溶剂中进行。所述有机溶剂可以为二氯甲烷、二氯乙烷、氯仿、甲醇、乙醇、丙酮、丁酮、四氢呋喃、二甲基亚砜、N,N-二甲基甲酰胺和乙腈中的至少一种。
根据本发明所述的方法,所述反应的条件可以包括反应温度为-100-100℃,优选10-50℃,进一步优选室温(即25℃左右);反应时间为1分钟-2天,优选1小时-1天,进一步优选4小时。
根据本发明所述的方法,该方法在碱的存在下进行,所述碱可以为碱金属的氢氧化物。例如可以为NaOH和/或KOH。所述碱的水溶液的浓度可以为0.01-10摩尔/升,优选0.5-5摩尔/升。
根据本发明所述的方法,所述的亲核试剂可以为碳原子为1-10的醇钠、醇钾、硫醇钠、硫醇钾、酚、酚钠和酚钾,或氰化钾、氰化钠、硫氰化钾、硫氢化钠中的至少一种。优选地,所述亲核试剂为甲醇钠、乙醇钠、氰化钾、苯酚钠、对甲苯酚钠、苯硫酚钠、对甲苯硫酚钠和对甲氧基苯硫酚钠中的至少一种。
根据本发明所述的方法,所述反应完成后,可以将获得的反应后混合物进行浓缩、沉淀后获得固体物质,再将获得的固体物质经过滤、洗涤和柱色谱分离后获得所述的锇过氧配合物。
根据本发明的第三个方面,本发明提供了上述的锇过氧配合物在催化醇氧化中的应用。
根据本发明,所述在氧化醇制备醛或酮中的应用包括选用反应温度为0-150℃,优选反应温度为40-100℃,最优选反应温度为80。℃所选用催化剂的量为0.1-8mol%,优选2-6mol%,更优选4mol%。所选用的氧气压力为0.1-0.5 MPa,优选的0.15 MPa。所选用的反应时间为1小时-2天,优选5小时-1天,进一步优选12小时。
根据本发明,所述在氧化醇制备醛或酮中的应用包括选用的有机溶剂为乙腈、氯仿、二氯甲烷、1,2-二氯乙烷、四氢呋喃,N,N-二甲基甲酰胺,二甲基亚砜中的任意一种,优选有机溶剂为二氯甲烷、1,2-二氯乙烷、氯仿,最优选有机溶剂为1,2-二氯乙烷。
根据本发明,所述在氧化醇制备醛或酮中的应用包括碱可以为无机碱或有机碱,优选为甲胺、乙胺、乙二胺、二甲胺、三甲胺、三乙胺、丙胺、异丙胺、1,3-丙二胺、1,2-丙二胺、三丙胺、丁胺、异丁胺、叔丁胺、己胺、辛胺、苯胺、苄胺、环己胺、吡啶、DBU、Na2CO3、K2CO3、NaHCO3、PhCOONa、乙酸钠、磷酸钾和碳酸钾中的一种或多种,进一步优选为碳酸钾。
根据本发明,所述在氧化醇制备醛或酮中的应用,所述的醇具有式(V)所示的结构:
其中,R为选自取代或非取代的C4-10的杂化化合物、取代或非取代的C4-10的非杂环化合物和C1-C20的脂肪基中的任意一种;R′为选自氢、取代或非取代的C4-10的杂化化合物、取代或非取代的C4-10的非杂环化合物和C1-C20的脂肪基中的任意一种;R′与R相同或不同;所述取代基为C1-6的烷基。
以下将通过具体的实施例对本发明进行详细描述。
以下制备例和实施例中,配合物A可以按照文献C.Zhu,S.Li,M.Luo,X.Zhou,Y.Niu,M.Lin,J.Zhu*,Z.Cao,X.Lu,T.Wen,Z.Xie,P.Schleyer,H.Xia*,Stabilization ofanti-aromatic and strained five-membered rings with a transition metal,NatureChemistry.2013,5,698–703中的方法制备得到。
例如可以按照如下方法制备得到配合物A:
称取12g氯锇酸钾(K2OsCl6)和48g三苯基膦(PPh3)于1000mL反应瓶中。然后加入320mL异丙醇,加热使固体全部溶解(约70℃)。加入200mL去离子水,将温度升高至100℃,开始回流12小时。然后在90℃条件下过滤得到OsCl2(PPh3)3。取6g OsCl2(PPh3)3于100mL反应瓶中,在氮气氛围中,加入40mL四氢呋喃,使OsCl2(PPh3)3溶解。称取422.2mg(5.272mmol)1,4-戊二炔-3-醇(购自湖北巨胜科技有限公司)溶解在10mL的THF中,然后注入上述溶液。搅拌10min,有黄色沉淀析出,用针桥过滤,将获得的固体先用THF洗一次,再用无水乙醚洗一次,抽干得黄白色固体。将获得的黄白色固体与2mL丙炔酸甲酯室温下反应2h,浓缩、柱色谱(柱色谱填料为100-200目中性氧化铝,洗脱剂为:二氯甲烷/甲醇=30/1体积比)分离后,减压浓缩得到配合物A。
所获得的配合物A的波谱数据如下:1H-NMR plus 1H-13C HSQC(500.1MHz,CDCl3):δ=14.25(s,1H,H7),9.27(s,1H,H5),8.32(s,1H,H3),3.68(s,3H,COOCH3),7.87–6.93ppm(m,45H,other aromatic protons).31P-NMR(202.5MHz,CDCl3):δ=6.54(t,JP-P=4.9Hz,CPPh3),3.75ppm(d,JP-P=4.9Hz,OsPPh3).13C-NMR plus DEPT-135and 1H-13C HSQC(125.8MHz,CD2Cl2):δ=324.5(td,JP-C=14.5Hz,JP-C=13.6Hz,C1),227.9(br,C7),182.0(d,JP-C=22.8Hz,C4),163.2(s,COOCH3,confirmed by 1H-13C HMBC),158.5(d,JP-C=15.2Hz,C3),155.6(s,C6),154.3(s,C5),119.1(d,JP-C=90.9Hz,C2),51.6(s,COOCH3),135.4–127.8ppm(m,other aromatic carbons).HRMS(ESI):m/z calcd for[C63H51ClO2OsP3]+,1159.2394;found,1159.2404.
制备例1
本制备例用以说明式(I)所示的锇过氧配合物的制备方法。
其中,[Os]为Os(PPh3)2,为三苯基膦阳离子,BPh4 -为四苯硼阴离子,Cl-为氯离子,Me为甲基。
将1mmol的配合物A(该配合物A对应于上述所提到的式(III)所示的配合物,其中,R3为MeOOC-,R2 +为三苯基膦阳离子M-为Cl-),3mmol的甲醇钠(CH3ONa)置于50mL反应瓶中,于氧气氛下注入20mL甲醇获得混合液;将获得的混合液在室温下反应4小时后,加入5mmol的四苯硼钠(NaBPh4),立刻析出大量固体。将析出的固体分别经水、甲醇、乙醚洗涤,再经过滤得到式(I-1)所示的锇过氧配合物,其中,式(I-1)对应于配合物:
所获得的锇过氧配合物的波谱数据如下:1H-NMR(400MHz,CD2Cl2):δ=13.17(q,JP-H=3.0Hz,1H,H7),8.70(d,JP-H=3.2Hz,1H,H5),8.38(d,JP-H=5.8Hz,1H,H3),3.92(s,3H,OCH3),3.55(s,3H,COOCH3),7.77-6.86ppm(m,45H,PPh3).31P-NMR(162MHz,CD2Cl2):δ=11.92(s,CPPh3),-16.25ppm(s,OsPPh3).13C-NMR(100MHz,CD2Cl2):δ=239.52(t,JP-C=8.1Hz,C1),214.60(t,JP-C=9.6Hz,C7),191.05(d,JP-C=24.4Hz,C4),162.35(s,COOCH3)161.38(d,JP-C=15.5Hz,C3),157.30(s,C5),130.38(d,JP-C=54.0Hz,C2),150.96(s,C6),62.93(s,OCH3),51.09(s,COOCH3),119.37-135.84ppm(m,PPh3).HRMS(ESI):m/z calcd for[C64H54O5OsP3]+,1187.2793;found,1187.2803.
制备例2
本制备例用以说明式(II)所示的锇过氧配合物的制备方法。
将0.1mmol的配合物I-1溶于10mL二氯甲烷/丙酮=1/1体积比的混合溶液中,然后加入0.50mmol氢氧化钠(NaOH)和0.1mL水获得混合液,将混合液在室温下搅拌1天后过滤,滤液浓缩至2mL,然后加入30mL正己烷作为沉淀剂。将析出的固体经过滤、洗涤和柱色谱分离(柱色谱填料为100-200目中性氧化铝,洗脱剂为:二氯甲烷/丙酮=20/1体积比)得到式(II-1)所示的锇过氧配合物,其中,式(I-1)对应于配合物:
所获得的锇过氧配合物的波谱数据如下:1H-NMR(400MHz,CD2Cl2):δ=13.29(s,1H,H7),31P NMR(161.9MHz,CD2Cl2):δ=–11.03ppm(s,OsPPh3).HRMS(ESI):m/z calcd for[C46H40NaO5OsP2+Na+],949.1858;found,949.1848.
如图1所示,图1为上述制备例2制备得到的式II-1所示的锇过氧配合物的高分辨质谱图,使用Bruker En Apex-Ultra 7.0T FT-MS测试。
如图2所示,图2为上述制备例2制备得到的式II-1所示的锇过氧配合物的X-射线衍射晶体结构图,使用Oxford Gemini S Ultra CCD Area Detector测试。
其中,在图2中反应示意图为:
其中,
实施例1
本实施例在于说明所述的锇过氧配合物在催化醇氧化中的应用。
向带有螺旋帽和磁力搅拌子的50mL反应管中,加入苯甲醇(0.3mmol),碳酸钾(0.6mmol),I-1(6mol%),1,2-二氯乙烷(1.5mL)。向反应液中通入氧气,并维持氧气压力为0.15MPa;于80℃下,加热12小时;反应结束后,将反应液冷却至室温,通过200-300目硅胶柱分离,石油醚:二氯甲烷=1:1为洗脱剂,减压除去有机溶剂得到苯甲醛,产物为无色液体,收率为88%。
1H NMR(500MHz,CDCl3):δ(ppm)=9.86(s,1H),7.72(d,J=6.9Hz,2H),7.46(tt,J=7.4,1.3Hz,1H),7.36(t,J=7.4Hz,2H);13C NMR(125MHz,CDCl3):δ(ppm)=192.30,136.40,134.40,129.66,128.96.
实施例2
本实施例在于说明所述的锇过氧配合物在催化醇氧化中的应用。
向带有螺旋帽和磁力搅拌子的50mL反应管中,加入对甲基苯甲醇(0.3mmol),碳酸钾(0.6mmol),I-1(6mol%),1,2-二氯乙烷(1.5mL)。向反应液中通入氧气,并维持氧气压力为0.15MPa;于80℃下,加热12小时;反应结束后,将反应液冷却至室温,通过200-300目硅胶柱分离,石油醚:二氯甲烷=1:1为洗脱剂,减压除去有机溶剂得到对甲基苯甲醛,产物为无色液体,收率为90%。
1H NMR(400MHz,CDCl3):δ(ppm)=9.95(s,1H),7.77(d,J=7.7Hz,2H),7.32(d,J=7.7Hz,2H),2.43ppm(s,3H);13C NMR(100MHz,CDCl3):δ(ppm)=192.13,145.67,134.30,129.96,129.82,22.00.
实施例3
本实施例在于说明所述的锇过氧配合物在催化醇氧化中的应用。
向带有螺旋帽和磁力搅拌子的50mL反应管中,加入对甲氧基苯甲醇(0.3mmol),碳酸钾(0.6mmol),I-1(6mol%),1,2-二氯乙烷(1.5mL)。向反应液中通入氧气,并维持氧气压力为0.15MPa;于80℃下,加热12小时;反应结束后,将反应液冷却至室温,通过200-300目硅胶柱分离,石油醚:二氯甲烷=1:1为洗脱剂,减压除去有机溶剂得到对甲氧基苯甲醛,产物为无色液体,收率为89%。
1H NMR(400MHz,CDCl3):δ(ppm)=9.86(s,1H),7.81(d,J=8.6Hz,2H),6.98(d,J=8.6Hz,2H),3.86(s,3H);13C NMR(100MHz,CDCl3):δ(ppm)=190.91,164.68,132.05,129.99,114.38,55.65.
实施例4
本实施例在于说明所述的锇过氧配合物在催化醇氧化中的应用。
向带有螺旋帽和磁力搅拌子的50mL反应管中,加入对氯苯甲醇(0.3mmol),碳酸钾(0.6mmol),I-1(5mol%),1,2-二氯乙烷(1.5mL)。向反应液中通入氧气,并维持氧气压力为0.15MPa;于80℃下,加热12小时;反应结束后,将反应液冷却至室温,通过200-300目硅胶柱分离,石油醚:二氯甲烷=1:1为洗脱剂,减压除去有机溶剂得到对氯苯甲醛,产物为白色固体,收率为83%。
1H NMR(400MHz,CDCl3):δ(ppm)=9.97(s,1H),7.81(d,J=8.3Hz,2H),7.50(d,J=8.3Hz,2H);13C NMR(100MHz,CDCl3):δ(ppm)=190.97,141.04,134.79,131.01,129.56.
实施例5
本实施例在于说明所述的锇过氧配合物在催化醇氧化中的应用。
向带有螺旋帽和磁力搅拌子的50mL反应管中,加入对硝基苯甲醇(0.3mmol),碳酸钾(0.6mmol),I-1(4mol%),1,2-二氯乙烷(1.5mL)。向反应液中通入氧气,并维持氧气压力为0.15MPa;于80℃下,加热12小时;反应结束后,将反应液冷却至室温,通过200-300目硅胶柱分离,石油醚:二氯甲烷=1:1为洗脱剂,减压除去有机溶剂得到对硝基苯甲醛,产物为白色固体,收率为95%。
1H NMR(400MHz,CDCl3):δ(ppm)=10.15(s,1H),8.38(d,J=8.7Hz,2H),8.07(d,J=8.7Hz,2H);13C NMR(100MHz,CDCl3):δ(ppm)=190.45,151.17,140.12,130.59,124.39.
实施例6
本实施例在于说明所述的锇过氧配合物在催化醇氧化中的应用。
向带有螺旋帽和磁力搅拌子的50mL反应管中,加入1-萘醇(0.3mmol),碳酸钾(0.6mmol),I-1(6mol%),1,2-二氯乙烷(1.5mL)。向反应液中通入氧气,并维持氧气压力为0.15MPa;于80℃下,加热12小时;反应结束后,将反应液冷却至室温,通过200-300目硅胶柱分离,石油醚:二氯甲烷=1:1为洗脱剂,减压除去有机溶剂得到1-萘醛,产物为淡黄色固体,收率为92%。
1H NMR(400MHz,CDCl3):δ(ppm)=10.39(s,1H),9.26(d,J=8.4Hz,1H),8.08(d,J=8.1Hz,1H),7.97(d,J=7.0Hz,1H),7.91(d,J=8.1Hz,1H),7.69(m,1H),7.60(m,2H);13CNMR(100MHz,CDCl3):δ(ppm)=193.66,136.80,135.38,133.78,131.44,130.58,129.15,128.56,127.04,124.95.
实施例7
本实施例在于说明所述的锇过氧配合物在催化醇氧化中的应用。
向带有螺旋帽和磁力搅拌子的50mL反应管中,加入1-芘醇(0.3mmol),碳酸钾(0.6mmol),I-1(5mol%),1,2-二氯乙烷(1.5mL)。向反应液中通入氧气,并维持氧气压力为0.15MPa;于80℃下,加热12小时;反应结束后,将反应液冷却至室温,通过200-300目硅胶柱分离,石油醚:二氯甲烷=2:1为洗脱剂,减压除去有机溶剂得到1-芘醛,产物为黄色固体,收率为98%。
1H NMR(400MHz,CDCl3):δ(ppm)=10.58(s,1H),9.12(d,J=9.2Hz,1H),8.16(d,J=7.7Hz,1H),8.11(d,J=7.7Hz,2H),8.04(d,J=9.2Hz,1H)8.00-7.93(m,3H),7.82(d,J=8.8Hz,1H);13C NMR(100MHz,CDCl3):δ(ppm)=192.78,135.12,130.91,130.65,130.41,130.37,130.09,127.01,126.91,126.83,126.61 126.33,124.21,124.15,123.65,122.62.
实施例8
本实施例在于说明所述的锇过氧配合物在催化醇氧化中的应用。
向带有螺旋帽和磁力搅拌子的50mL反应管中,加入1-苯乙醇(0.3mmol),碳酸钾(0.6mmol),I-1(8mol%),1,2-二氯乙烷(1.5mL)。向反应液中通入氧气,并维持氧气压力为0.15MPa;于80℃下,加热12小时;反应结束后,将反应液冷却至室温,通过200-300目硅胶柱分离,石油醚:二氯甲烷=1:1为洗脱剂,减压除去有机溶剂得到1-苯乙酮,产物为无色液体,收率为61%。
1H NMR(400MHz,CDCl3):δ(ppm)=7.95(d,J=6.9Hz,2H),7.55(t,J=6.9Hz,1H),7.45(t,J=7.3Hz,2H),2.60(s,3H);13C NMR(100MHz,CDCl3):δ(ppm)=198.30,137.21,133.22,128.68,128.41,26.73.
实施例9
本实施例在于说明所述的锇过氧配合物在催化醇氧化中的应用。
向带有螺旋帽和磁力搅拌子的50mL反应管中,加入1-茚醇(0.3mmol),碳酸钾(0.6mmol),I-1(8mol%),1,2-二氯乙烷(1.5mL)。向反应液中通入氧气,并维持氧气压力为0.15MPa;于80℃下,加热12小时;反应结束后,将反应液冷却至室温,通过200-300目硅胶柱分离,石油醚:二氯甲烷=1:1为洗脱剂,减压除去有机溶剂得到1-茚酮,产物为白色固体,收率为61%。
1H NMR(400MHz,CDCl3):δ(ppm)=7.76(d,J=7.8Hz,1H),7.58(td,J=7.5,1.1Hz,1H),7.48(d,J=7.7Hz,1H),7.37(td,J=7.5,1.0Hz,1H),3.15(t,J=5.9Hz,2H),2.69(t,J=5.9Hz,2H);13C NMR(100MHz,CDCl3):δ(ppm)=207.22,155.30,137.24,134.74,127.43,126.83,123.88,36.36,25.95.
实施例10
本实施例在于说明所述的锇过氧配合物在催化醇氧化中的应用。
向带有螺旋帽和磁力搅拌子的50mL反应管中,加入二苯甲醇(0.3mmol),碳酸钾(0.6mmol),I-1(4mol%),1,2-二氯乙烷(1.5mL)。向反应液中通入氧气,并维持氧气压力为0.15MPa;于80℃下,加热12小时;反应结束后,将反应液冷却至室温,通过200-300目硅胶柱分离,石油醚:二氯甲烷=1:1为洗脱剂,减压除去有机溶剂得到二苯甲酮,产物为白色固体,收率为97%。
1H NMR(400MHz,CDCl3):δ(ppm)=7.70(d,J=7.3Hz,4H),7.48(t,J=7.3Hz,2H),7.37(t,J=7.5Hz,4H);13C NMR(100MHz,CDCl3):δ(ppm)=196.77,137.59,132.45,130.07,128.30.
实施例11
本实施例在于说明所述的锇过氧配合物在催化醇氧化中的应用。
向带有螺旋帽和磁力搅拌子的50mL反应管中,加入2-噻吩甲醇(0.3mmol),碳酸钾(0.6mmol),I-1(6mol%),1,2-二氯乙烷(1.5mL)。向反应液中通入氧气,并维持氧气压力为0.15MPa;于80℃下,加热12小时;反应结束后,将反应液冷却至室温,通过200-300目硅胶柱分离,石油醚:二氯甲烷=1:1为洗脱剂,减压除去有机溶剂得到2-噻吩甲醛,产物为淡黄色油状物,收率为79%。
1H NMR(400MHz,CDCl3):δ(ppm)=9.93(d,J=1.2Hz,1H),7.76(m,2H),7.20(dd,J=4.8,3.7Hz,1H);13C NMR(100MHz,CDCl3):δ(ppm)=183.13,144.11,136.47,135.24,128.43.
实施例12
本实施例在于说明所述的锇过氧配合物在催化醇氧化中的应用。
向带有螺旋帽和磁力搅拌子的50mL反应管中,加入2-呋喃甲醇(0.3mmol),碳酸钾(0.6mmol),I-1(6mol%),1,2-二氯乙烷(1.5mL)。向反应液中通入氧气,并维持氧气压力为0.15MPa;于80℃下,加热12小时;反应结束后,将反应液冷却至室温,通过200-300目硅胶柱分离,石油醚:二氯甲烷=1:1为洗脱剂,减压除去有机溶剂得到2-呋喃甲醛,产物为无色油状物,GC收率为83%。
1H NMR(400MHz,CDCl3):δ(ppm)=9.60(s,1H),7.63(s,1H),7.19(s,1H),6.54(s,1H);13C NMR(100MHz,CDCl3):δ(ppm)=178.02,153.19,148.18,120.98,112.70.
根据制备例1和制备例2制备的锇过氧配合物,本发明提供的锇过氧配合物具有高的热、空气、水和光照稳定性以及制备过程简单等特点;以及实施例1-12是以该锇过氧配合物为催化剂,氧气为氧化剂,应用于氧化一系列醇制备羰基化合物时,具有高选择性、较宽的底物普适性以及条件温和等优点。
以上详细描述了本发明的优选实施方式,但是,本发明并不限于上述实施方式中的具体细节,在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,这些简单变型均属于本发明的保护范围。
此外,本发明的各种不同的实施方式之间也可以进行任意组合,只要其不违背本发明的思想,其同样应当视为本发明所公开的内容。
Claims (15)
3.权利要求1或2所述配合物的制备方法,其特征在于,所述方法包括:
使用式(III)所示的配合物与亲核试剂在氧气存在的条件下反应制备式(I)所示的配合物;
使用式(IV)所示的配合物与亲核试剂在氧气存在的条件下反应制备式(II)所示的配合物,或者通过将式(I)所示的配合物在强碱的水溶液中水解来制备式(II)所示的配合物;
其中,
所述碱为碱金属的氢氧化物;所述碱的水溶液的浓度为0.01-10摩尔/升;
所述亲核试剂为碳原子数为1-10的醇钠、醇钾、硫醇钠、硫醇钾、酚、酚钠和酚钾,氰化钾、氰化钠、硫氰化钾和硫氢化钠中的至少一种;
其中,M-、R2 +、[Os]以及式(III)和式(IV)R3与权利要求1中所述的M-、R2 +、[Os]以及R3相同。
4.根据权利要求3所述的方法,其中,所述碱的水溶液的浓度为0.5-5摩尔/升;所述亲核试剂为甲醇钠、乙醇钠、氰化钾、苯酚钠、对甲苯酚钠、苯硫酚钠、对甲苯硫酚钠和对甲氧基苯硫酚钠中的至少一种。
5.权利要求1或2所述的锇过氧配合物或权利要求3或4所述的制备方法制备的锇过氧配合物在催化醇氧化中的应用,其中,以所述的锇过氧配合物为催化剂,以氧气为氧化剂。
6.根据权利要求5所述的应用,其中,在催化醇氧化中,所述催化剂的用量为0.1-8mol%;以及在温度为0-150℃,所述的氧气在压力为0.1-0.5MPa的条件下进行1小时-2天。
7.根据权利要求6所述的应用,其中,所述催化剂的用量为2-6mol%,以及在温度为40-100℃,所述的氧气在压力为0.15MPa的条件下进行5小时-1天。
8.根据权利要求7所述的应用,其中,所述催化剂的用量为4mol%;以及在温度为80℃的条件下进行12小时。
9.根据权利要求5所述的应用,其中,在催化醇氧化中,在有机溶剂的存在下进行,所述的有机溶剂为乙腈、氯仿、二氯甲烷、1,2-二氯乙烷、四氢呋喃,N,N-二甲基甲酰胺和二甲基亚砜中的一种或多种。
10.根据权利要求9所述的应用,其中,所述有机溶剂为二氯甲烷、1,2-二氯乙烷和氯仿中的一种或多种。
11.根据权利要求10所述的应用,其中,所述有机溶剂为1,2-二氯乙烷。
12.根据权利要求5所述的应用,其中,在醛或酮的制备中,在碱的存在下进行,所述碱为无机碱或有机碱。
13.根据权利要求12所述的应用,其中,所述碱为甲胺、乙胺、乙二胺、二甲胺、三甲胺、三乙胺、丙胺、异丙胺、1,3-丙二胺、1,2-丙二胺、三丙胺、丁胺、异丁胺、叔丁胺、己胺、辛胺、苯胺、苄胺、环己胺、吡啶、DBU、Na2CO3、K2CO3、NaHCO3、PhCOONa、乙酸钠、磷酸钾和碳酸钾中的一种或多种。
14.根据权利要求13所述的应用,其中,所述碱为碳酸钾。
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