CN109956970A - 联苯型三齿配体钌络合物及其制备方法和应用 - Google Patents
联苯型三齿配体钌络合物及其制备方法和应用 Download PDFInfo
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- CN109956970A CN109956970A CN201711439046.3A CN201711439046A CN109956970A CN 109956970 A CN109956970 A CN 109956970A CN 201711439046 A CN201711439046 A CN 201711439046A CN 109956970 A CN109956970 A CN 109956970A
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- Prior art keywords
- tridentate ligand
- biphenyl type
- ruthenium complex
- compound
- hydrogenation
- Prior art date
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000003446 ligand Substances 0.000 title claims abstract description 64
- 235000010290 biphenyl Nutrition 0.000 title claims abstract description 46
- 239000004305 biphenyl Substances 0.000 title claims abstract description 45
- 239000012327 Ruthenium complex Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 150000001875 compounds Chemical class 0.000 claims abstract description 53
- 150000002148 esters Chemical class 0.000 claims abstract description 47
- -1 alcohol compound Chemical class 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 8
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims description 34
- 239000007787 solid Substances 0.000 claims description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 24
- 239000002585 base Substances 0.000 claims description 24
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 24
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 125000001424 substituent group Chemical group 0.000 claims description 14
- 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 14
- 239000002904 solvent Substances 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 150000002596 lactones Chemical class 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052701 rubidium Inorganic materials 0.000 claims description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 125000001072 heteroaryl group Chemical group 0.000 claims description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- HBIHVBJJZAHVLE-UHFFFAOYSA-L dibromoruthenium Chemical compound Br[Ru]Br HBIHVBJJZAHVLE-UHFFFAOYSA-L 0.000 claims description 8
- HRSOSLBSWOHVPK-UHFFFAOYSA-L diiodoruthenium Chemical compound I[Ru]I HRSOSLBSWOHVPK-UHFFFAOYSA-L 0.000 claims description 8
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 125000002541 furyl group Chemical group 0.000 claims description 6
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 6
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 125000004076 pyridyl group Chemical group 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 125000001544 thienyl group Chemical group 0.000 claims description 6
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- NCDCLPBOMHPFCV-UHFFFAOYSA-N hexyl hexanoate Chemical compound CCCCCCOC(=O)CCCCC NCDCLPBOMHPFCV-UHFFFAOYSA-N 0.000 claims description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- NUKZAGXMHTUAFE-UHFFFAOYSA-N methyl hexanoate Chemical compound CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 claims description 4
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 2
- NOMHBBFEJSVGSC-UHFFFAOYSA-N 1-chloro-2-(2-chloroethylsulfinyl)ethane Chemical compound ClCCS(=O)CCCl NOMHBBFEJSVGSC-UHFFFAOYSA-N 0.000 claims description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 2
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 claims description 2
- QGLBZNZGBLRJGS-UHFFFAOYSA-N Dihydro-3-methyl-2(3H)-furanone Chemical compound CC1CCOC1=O QGLBZNZGBLRJGS-UHFFFAOYSA-N 0.000 claims description 2
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 claims description 2
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 2
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical group [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- YGXMUPKIEHNBNQ-UHFFFAOYSA-J benzene;ruthenium(2+);tetrachloride Chemical compound Cl[Ru]Cl.Cl[Ru]Cl.C1=CC=CC=C1.C1=CC=CC=C1 YGXMUPKIEHNBNQ-UHFFFAOYSA-J 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- JYHHJVKGDCZCCL-UHFFFAOYSA-J carbon monoxide;dichlororuthenium Chemical compound [O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].Cl[Ru]Cl.Cl[Ru]Cl JYHHJVKGDCZCCL-UHFFFAOYSA-J 0.000 claims description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 2
- WIWBLJMBLGWSIN-UHFFFAOYSA-L dichlorotris(triphenylphosphine)ruthenium(ii) Chemical compound [Cl-].[Cl-].[Ru+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 WIWBLJMBLGWSIN-UHFFFAOYSA-L 0.000 claims description 2
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- VMPHSYLJUKZBJJ-UHFFFAOYSA-N lauric acid triglyceride Natural products CCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCC)COC(=O)CCCCCCCCCCC VMPHSYLJUKZBJJ-UHFFFAOYSA-N 0.000 claims description 2
- 229940095102 methyl benzoate Drugs 0.000 claims description 2
- 229940057867 methyl lactate Drugs 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- XSXHWVKGUXMUQE-UHFFFAOYSA-N osmium dioxide Inorganic materials O=[Os]=O XSXHWVKGUXMUQE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- 125000003367 polycyclic group Chemical group 0.000 claims description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- WQKGAJDYBZOFSR-UHFFFAOYSA-N potassium;propan-2-olate Chemical compound [K+].CC(C)[O-] WQKGAJDYBZOFSR-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000003883 substance clean up Methods 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 150000003462 sulfoxides Chemical class 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000002827 triflate group Chemical group FC(S(=O)(=O)O*)(F)F 0.000 claims description 2
- 238000003828 vacuum filtration Methods 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 2
- 239000001605 (5-methyl-2-propan-2-ylcyclohexyl) acetate Substances 0.000 claims 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims 1
- XHXUANMFYXWVNG-UHFFFAOYSA-N D-menthyl acetate Natural products CC(C)C1CCC(C)CC1OC(C)=O XHXUANMFYXWVNG-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- XHXUANMFYXWVNG-ADEWGFFLSA-N Menthyl acetate Natural products CC(C)[C@@H]1CC[C@@H](C)C[C@H]1OC(C)=O XHXUANMFYXWVNG-ADEWGFFLSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 229940058352 levulinate Drugs 0.000 claims 1
- 150000004702 methyl esters Chemical class 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- LMHHRCOWPQNFTF-UHFFFAOYSA-N s-propan-2-yl azepane-1-carbothioate Chemical compound CC(C)SC(=O)N1CCCCCC1 LMHHRCOWPQNFTF-UHFFFAOYSA-N 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000007210 heterogeneous catalysis Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000007172 homogeneous catalysis Methods 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 48
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 26
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- 238000004679 31P NMR spectroscopy Methods 0.000 description 13
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 13
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 239000012300 argon atmosphere Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000010189 synthetic method Methods 0.000 description 8
- 238000000132 electrospray ionisation Methods 0.000 description 7
- 238000009905 homogeneous catalytic hydrogenation reaction Methods 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002274 desiccant Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 231100000989 no adverse effect Toxicity 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 238000010257 thawing Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CZLJVZVIMFMGCH-UHFFFAOYSA-N (2-aminophenoxy)boronic acid Chemical compound NC1=CC=CC=C1OB(O)O CZLJVZVIMFMGCH-UHFFFAOYSA-N 0.000 description 1
- XIONUQPOXCUMMB-UHFFFAOYSA-N (2-bromophenyl)-diphenylphosphane Chemical compound BrC1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 XIONUQPOXCUMMB-UHFFFAOYSA-N 0.000 description 1
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 1
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- ZFEZIAPMHMZNRS-UHFFFAOYSA-N 2-$l^{1}-sulfanyl-2-methylpropane Chemical compound CC(C)(C)[S] ZFEZIAPMHMZNRS-UHFFFAOYSA-N 0.000 description 1
- ILLCGAJCYFLVSV-UHFFFAOYSA-N 2-butylsulfanylacetic acid Chemical compound CCCCSCC(O)=O ILLCGAJCYFLVSV-UHFFFAOYSA-N 0.000 description 1
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 description 1
- BUTKIHRNYUEGKB-UHFFFAOYSA-N 3,3-dimethylbutanoyl chloride Chemical compound CC(C)(C)CC(Cl)=O BUTKIHRNYUEGKB-UHFFFAOYSA-N 0.000 description 1
- WDQLFLIUEDVQKH-UHFFFAOYSA-N C1(=CC=CC=C1)[B].[Na] Chemical compound C1(=CC=CC=C1)[B].[Na] WDQLFLIUEDVQKH-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002477 CuCr2O4 Inorganic materials 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical class OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 238000004639 Schlenk technique Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 229940125797 compound 12 Drugs 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000011903 deuterated solvents Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000010805 inorganic waste Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000002646 long chain fatty acid esters Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- PPFNAOBWGRMDLL-UHFFFAOYSA-N methyl 2-ethoxyacetate Chemical class CCOCC(=O)OC PPFNAOBWGRMDLL-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- KZJPVUDYAMEDRM-UHFFFAOYSA-M silver;2,2,2-trifluoroacetate Chemical group [Ag+].[O-]C(=O)C(F)(F)F KZJPVUDYAMEDRM-UHFFFAOYSA-M 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010729 system oil Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
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Abstract
本发明涉及一种新型联苯型三齿配体及其钌络合物的制备方法和在酯类化合物氢化为醇类化合物反应中的应用。使用联苯型三齿配体钌络合物催化氢化酯类化合物为醇类化合物方法的特征在于:以酯类化合物物质的量的0.001~0.1mol%的联苯型三齿配体钌络合物为催化剂,加入酯类化合物物质的量的1~10mol%的碱,在60~100℃和30~70MPa氢气压力条件下催化氢化酯类化合物为相应的醇类化合物。本发明的联苯型三齿配体及其钌络合物制备方便,结构稳定,在酯类化合氢化反应中表现出优良的催化活性。本发明克服了现有均相或非均相催化体系氢化酯类化合物需要高温高压等苛刻的反应条件和催化剂用量高的缺点,催化剂用量小,反应条件温和,反应的选择性好,提高了生产体系的经济性和安全性。
Description
技术领域
本发明涉及一种新型联苯型三齿配体钌络合物及其制备方法和在酯类化合物氢化为醇类化合物反应中的应用。
背景技术
酯类化合物还原制备醇类化合物是有机化学中的重要转化,无论在基础科学研究还是在工业生产上都有重要的意义。酯类化合物还原为醇类化合物在实验室中常用的是当量的还原负氢试剂如四氢铝锂等,而这些负氢试剂在后处理时会产生大量的无机废物,并且这些活泼的负氢试剂在大量使用时会带来安全隐患,限制了其在工业生产上的应用。催化氢化还原酯类化合物为醇类化合物是一种绿色、高原子经济性的方法,因此发展催化氢化酯类化合物的催化剂的具有重要的科学意义和应用价值。
目前,使用非均相催化剂氢化酯类化合物为醇类化合物通常需要高温高压的苛刻条件,相应的报道可以参考最近的综述文章(Chem.Soc.Rev.2015,44,3808-3833)及其中所引文献。例如美国专利US5155086报道了使用CuO/CuCr2O4为催化剂,在反应温度为200~300℃,氢气压力为20~30MPa条件下催化氢化长链脂肪酸酯制备长链脂肪醇的方法。由于非均相催化氢化体系普遍存在着反应条件苛刻(例如:高温、高压)的问题,导致生产成本高,不利于规模化生产。
酯类化合物的均相催化氢化催化剂的发展无论在学术界还是在工业界都得到了关注,而发展合适的催化体系是酯类化合物均相催化氢化的核心。最近几年,基于钌的酯类化合物均相催化氢化催化剂得到了较多的研究,相应的报道可以参见最近的综述文章(Org.Process Res.Dev.2014,18,289-302)和其中所引文献。发展高效、实用的催化体系应用于普通羧酸酯、内酯以及甘油脂肪酸酯的氢化具有重要的实用价值。特别是可以将反应过程的温度控制在20~100℃,反应的催化剂用量控制在0.05~0.1mol%,反应的氢气压力控制在0.1~5MPa。工业界也有较多的酯类化合物均相催化氢化的专利报道,其中含有氨基膦配位基团的三齿或四尺钳型配体的钌络合物应用最为广泛(相应的报道见:US20100280273A1,WO2012052996A2,WO2014036650,CN103980317A,Green Chem.2014,16,4081-4085)。总体来说,酯类化合物的均相催化氢化可以在相对较温和的条件下进行,但大多数报道的反应温度仍需要100℃及以上,适宜催化剂的配体合成繁琐,通常需要4-5步,且需要用到敏感的化学试剂,从而增加了生产成本,不利于工业化生产。因此,发展高效的酯类化合物均相催化氢化催化剂显得尤为重要。
发明内容
本发明的目的在于提出一种易于合成的新型联苯三齿配体钌络合物及其制备方法和在酯类化合物氢化为醇类化合物反应中的应用。将联苯型三齿配体与金属钌前体直接将合成制备的固体联吡啶四齿配体钌络合物作为催化剂应用于酯类化合物氢化制备醇类化合物的反应中。本发明的联苯型三齿配体钌络合物制备方便,结构稳定,在酯类化合氢化反应中表现出优异的催化活性。本发明克服了现有酯类化合物均相或非均相催化氢化体系需要高温高压反应条件和催化剂难以制备的缺点,催化剂易于合成且用量小,反应条件温和,反应的选择性好,提高了生产体系的实用性和经济性。
本发明所提供的新型联吡啶四齿配体具有如I所示的结构通式:
其中,配位基团L1选自:PR1R2,配位基团L2选自:吡啶、CH2SR。
R、R1和R2可独立地选自C1~C8烷基、C3~C8环烷基、苯基、取代的苯基、1-萘基、2-萘基、杂芳基、苄基等对反应无不利影响的基团。所述的取代的苯基上的取代基为C1~C8烷基、C3~C8环烷基、苯基、烷氧基以及卤素等对反应无不利影响的基团,取代基数量为1~5;所述的杂芳基为呋喃基、噻吩基或吡啶基等;R1、R2可以相同,也可不同。R1、R2可并为C3~C8脂肪环或芳香环。
X1、X2可独立地选自H、C1~C8烷基、C3~C8环烷基、苯基、取代的苯基、1-萘基、2-萘基、杂芳基、苄基、卤素等对反应无不利影响的基团;所述的取代的苯基上的取代基为C1~C8烷基、C3~C8环烷基、苯基、烷氧基以及卤素等对反应无不利影响的基团,取代基数量为1~5;所述的杂芳基为呋喃基、噻吩基或吡啶基等;m=0~3,n=0~3;当m≥2时,两个相邻的X1可并为C3~C8脂肪环或芳香环;当n≥2时,两个相邻的X2可并为C3~C8脂肪环或芳香环;X1、X2可以相同,也可不同;
可选地,以上所述的C1~C8烷基为甲基、乙基、正丙基、异丙基、正丁基、叔丁基等;所述的C3~C8环烷基为环丙基、环丁基、环戊基、环己基等;所述的烷氧基为甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、叔丁氧基等。
本发明关于基团的定义均为本领域普通技术人员所熟知,在此及下文不再做详细的说明。
可选地,联吡啶四齿配体包括下面结构式所示:
本发明提供的合成制备的联苯型三齿配体钌络合物具有如II所示的结构通式:
其中,L1、L2、X1、X2、m、n的定义与通式I所述相同;Y,Z为H、Cl、Br、I、ClO4、PF6、BPh4、B(C6F5)4、BF4、BH4、OCOR、OCOCF3、OSO2R、OSO2CF3、CN、OR、NR2、SR、R2S(O)、CO、PR3;R为H、C1~C8烷基、C3~C8环烷基、苯基、取代的苯基、1-萘基、2-萘基、杂芳基、苄基;所述的取代的苯基上的取代基为C1~C8烷基、C3~C8环烷基、苯基、烷氧基以及卤素,取代基数量为1~5;所述的杂芳基为呋喃基、噻吩基或吡啶基;X,Y,Z相同或不同。
可选地,X,Y,Z为不同的Cl、CO、H或二甲基亚砜。
通式II中的联苯型三齿配体钌络合物可按如下方法由联苯型三齿配体与金属钌合成制备:
在二氯甲烷、四氢呋喃、甲苯、N,N-二甲基甲酰胺、二甲亚砜有机溶剂中,金属钌前体和相对于钌原子物质的量1.0~1.5倍量的所述联苯型三齿配体,在25~120℃反应4~16小时,溶液旋转蒸发至原体积1/10;将浓缩的溶液在搅拌下加入乙醚或正己烷,析出白色或者黄色固体,真空抽滤,用乙醚或正己烷洗涤滤饼,滤饼真空干燥后得到固体联苯型三齿配体钌络合物。
所述的金属钌前体是RuCl3·nH2O、[RuCl2(CO)3]2、[Ru(cod)Cl2]n、[Ru(nbd)Cl2]n、[RuCl2(benzene)]2、[RuBr2(benzene)]2、[RuI2(benzene)]2、[RuCl2(η6-p-cymene)]2、[RuBr2(η6-p-cymene)]2、[RuI2(η6-p-cymene)]2、[RuCl2(mesitylene)]2、[RuBr2(mesitylene)]2、[RuI2(mesitylene)]2、RuCl2(PPh3)3,、RuBr2(PPh3)3、RuI2(PPh3)3、RuCl2(DMSO)4、Ru(H)Cl(CO)(PPh3)3,其中:cod=1,5-环辛二烯,nbd=2,5-降冰片二烯,DMSO=二甲亚砜。
可选地,合成制备的联苯型三齿配体钌络合物包括下面结构式所示:
通式II中X,Z为H或其它配阴离子时的联吡啶四齿配体钌络合物可以由X,Z为相同的卤素(Cl、Br、I)时的联吡啶四齿配体钌络合物与相应量的氢化钠、醋酸钠、高氯酸钠、四苯基硼钠、三氟醋酸银等无机盐交换阴离子原位生成得到相应的联吡啶四齿配体钌络合物溶液或合成制备得到相应的固体联吡啶四齿配体钌络合物。
本发明将联吡啶四齿配体与金属钌前体原位生成的联吡啶四齿配体钌络合物溶液或合成制备的固体联吡啶四齿配体钌络合物作为催化剂应用于酯类化合物催化氢化为醇类化合物的反应中,所适用的酯类化合物可以是脂肪族羧酸酯、芳香族羧酸酯、甲酸酯、碳酸酯和内酯等,可以含有一个或多个酯基,可以带有任意不影响氢化反应的取代基。
所述的酯类化合物如通式III所示:
其中,Ra、Rb可独立地选自C1~C30烷基、C3~C30环烷基、C2~C30烯基、C3~C30环烯基、芳基等,这些基团中可以含有任意不影响氢化反应的取代基,Ra、Rb可以相同,也可不同;Ra、Rb可以相连即形成环状的C4~C30的内酯,内酯环上可以含有任意不影响氢化反应的取代基,内酯环上合适位置的碳原子可以被O、N、S等杂原子取代,内酯环可以是单环,也可以是多环,所述的内酯可以是饱和内酯或不饱和内酯。
所述的醇类化合物如通式IV-a、IV-b所示:
Ra、Rb的定义与通式III中所述相同。当Ra、Rb未相连时所述的醇类化合物如IV-a、IV-b所示;当Ra、Rb相连时所述的醇类化合物是相应内酯还原后所得的二元醇;当氢化所用的酯类化合物中含有多个酯基时,所得的醇类化合物为相应的多元醇。
酯类化合物的非限制性实例包括苯甲酸甲酯、乙酸乙酯、乙二醇碳酸酯、乙酰丙酸甲酯、琥珀酸二甲酯、γ-丁内酯、γ-戊内酯、α-甲基-γ-丁内酯、乙醇酸甲酯、乳酸甲酯、甲氧基乙酸甲酯、月桂酸甲酯、硬脂酸甲酯、三月桂酸甘油酯、三硬脂酸甘油酯、草酸二甲酯、1,2-苯二甲酸甲酯、1,3-苯二甲酸甲酯、己酸甲酯、己酸己酯等。
本发明对酯类化合物的催化氢化应用的方法包括如下步骤:
在氩气或氮气保护下,将催化剂即联苯型三齿配体钌络合物和碱加入反应釜内管中,加入底物溶于相应溶剂的溶液,拧紧反应釜并用氢气小心置换3~5次,调节氢气压力至所需压力后,在合适温度下搅拌反应至压力不再变化,将反应釜恢复室温,缓慢释放剩余氢气。产物通过柱层析、蒸馏等常用有机化合物纯化方法进行分离提纯。
本发明使用联苯型三齿配体钌络合物催化氢化酯类化合物为醇类化合物方法的特征在于:催化剂用量为底物物质的量的0.001~0.1mol%,碱用量为底物物质的量的1~10mol%,氢气压力3~10MPa,反应温度为60~100℃,反应时间为1~64小时。
本发明对酯类化合物的催化氢化可以在无溶剂条件下进行,但优选使用溶剂。所用溶剂的非限制性实例为四氢呋喃、甲苯、甲醇和1,4-二氧六环等有机溶剂中的一种或其中几种的混合溶剂。
本发明对酯类化合物的催化氢化所用碱的非限制性实例为甲醇钠、乙醇钠、异丙醇钠、叔丁醇钠、甲醇钾、乙醇钾、异丙醇钾、叔丁醇钾等。所用碱可以直接加入到反应釜内管中或者溶解在相应溶剂中加入到反应釜内管中。
本发明将联苯型三齿配体与金属钌前体合成制备的固体联苯型三齿配体钌络合物作为催化剂应用于酯类化合物氢化制备醇类化合物的反应中。本发明的联苯型三齿配体及其钌络合物制备方便,结构稳定,在酯类化合氢化反应中表现出优异的催化活性,反应选择性好,产率高。本发明克服了现有酯类化合物均相或非均相催化氢化体系需要高温高压反应条件和高催化剂用量的缺点,催化剂用量小,反应条件温和,反应温度和压力远低于其他均相或非均相催化体系,反应的选择性好,提高了生产体系的经济性和安全性,具有广阔的应用前景。
具体实施方式
下述非限制性实施例可以使本领域的普通技术人员更全面地理解本发明,但不以任何方式限制本发明。实施例中未注明具体条件的实验方法,通常按照常规条件以及手册中所述的条件,或按照制造厂商所建议的条件;所用的材料、试剂等,如无特殊说明,均可从商业途径得到。
所有空气敏感化合物均在MBRAUN LABstar氩气氛围手套箱中称量并在真空线上严格按照标准Schlenk技术操作。1H NMR、13C NMR、31P NMR核磁共振谱分别由Bruker AV400核磁共振仪(工作频率分别为400MHz、101MHz和162MHz)测定,化学位移的单位是ppm,1HNMR谱用四甲基硅烷作为内标,13C NMR谱用所列出的氘代溶剂作为内标,31P NMR谱用85%H3PO4作为外标;高分辨质谱由APEXII型FT-ICR质谱仪测定,以ESI(电喷雾电离)或MALDI(基质辅助激光解吸附电离)为离子源;元素分析由Elementar Vario EL元素分析仪测定;单晶衍射由Rigaku 007 Saturn 70单晶衍射仪测定;气相色谱分析使用Agilent 7890A气相色谱仪。
实施例1
配体1的制备
2′-二苯基膦基-2-胺基-1,1′-联苯(13):在装有磁力搅拌子的干燥洁净的100mL封管中加入(2-溴苯基)-二苯基膦37a(1.2g,3.5mmol)、2-氨基苯硼酸(480mg,3.5mmol)、[1,1′-双(二苯基膦基)二茂铁]二氯化钯(143mg,0.18mmol)、无水磷酸钾(2.3g,11.5mmol)。将封管转移至氩气氛围的手套箱中,加入30mL无水1,4-二氧六环,将封管用旋塞封好后取出,油浴加热100-105℃反应16小时。停止加热,冷却至室温后,加入20mL水淬灭反应,以乙酸乙酯(20mL×3)萃取水相,有机相以饱和食盐水洗涤一次,无水硫酸钠干燥。抽滤除去干燥剂,滤液用旋转蒸发仪脱除溶剂,残余物经硅胶柱层析(石油醚/乙酸乙酯=5∶1)得到1.1g白色固体27a,收率86%,熔点:103~105℃。
1H NMR(400MHz,CDCl3)δ7.45(t,J=6.9Hz,1H),7.38-7.19(m,12H),7.18-7.11(m,2H),6.75-6.70(m,2H),6.62(t,J=7.4Hz,1H),3.44(s,2H).31P NMR(162MHz,CDCl3)δ-13.02(s).13C NMR(101MHz,CDCl3)δ144.7(d,J=30.7Hz),143.5,138.1(d,J=12.2Hz),137.5(d,J=12.4Hz),137.0(d,J=11.3Hz),134.1,133.9,133.8,131.1(d,J=3.0Hz),130.6(d,J=5.1Hz),129.4,128.8,128.5,128.4,128.4(d,J=3.8Hz),128.3,127.9,127.1(d,J=6.7Hz),117.8,115.3.HRMS(MALDI)Calcd for C24H21NP[M+H]+:354.1406;Found:354.1399.
2′-二苯基膦基-N-(吡啶-2-甲基)-2′-氨基-1,1′-联苯(1):在装有磁力搅拌子的干燥洁净的50mL Schlenk瓶中加入13(706mg,2.0mmol),NaBH(OAc)3(851mg,4.0mmol),置换成氮气氛围后,加入15mL 1,2-二氯乙烷,搅拌充分溶解后再加入吡啶-2-甲醛(257mg,2.4mmol)。室温搅拌反应4h,TLC监测反应。慢慢加入10mL饱和碳酸氢钠水溶液淬灭反应,水相用乙酸乙酯萃取(10mL×3),合并有机相,无水硫酸镁干燥。抽滤除去干燥剂,滤液用旋转蒸发仪脱除溶剂,残余物经硅胶柱层析(石油醚∶乙酸乙酯=2∶1)得到809mg白色固体1,两步收率78%,熔点:54~56℃。
1H NMR(400MHz,CDCl3)δ8.50(d,J=4.1Hz,1H),7.57(td,J=7.7,1.7Hz,1H),7.45(td,J=7.4,1.3Hz,1H),7.37-7.27(m,7H),7.24-7.10(m,10H),6.79(dd,J=7.4,1.5Hz,1H),6.59(td,J=7.4,0.9Hz,1H),6.46(d,J=8.0Hz,1H),4.30-4.22(m,3H).31P NMR(162MHz,CDCl3)δ-13.81(s).13C NMR(101MHz,CDCl3)δ159.3,149.1,144.8,136.6,134.3,133.9(d,J=2.3Hz),133.7(d,J=2.0Hz),130.9(d,J=5.2Hz),130.8(d,J=3.2Hz),129.5,128.9,128.5,128.4,128.4,128.3,128.2,128.0,121.8,121.1(d,J=3.0Hz),116.5,110.4,49.3.HRMS(MALDI)Calcd for C30H25N2P[M+H]+:445.1828;Found:445.1825.
实施例2
配体2的制备
合成方法同配体1,白色固体,两步收率74%,熔点:60~62℃。
1H NMR(400MHz,CDCl3)δ8.51(d,J=2.9Hz,1H),7.58(td,J=7.7,1.6Hz,1H),7.46-7.40(m,1H),7.36-7.29(m,3H),7.21-7.07(m,8H),6.84(d,J=8.5Hz,2H),6.80-6.73(m,3H),6.62-6.56(m,1H),6.51-6.46(m,1H),4.35(s,1H),4.27(dd,J=12.4,3.4Hz,2H),3.80(s,3H),3.76(s,3H).31P NMR(162MHz,CDCl3)δ-16.95(s).13C NMR(101MHz,CDCl3)δ160.0(d,J=2.7Hz),159.3,149.1,144.7,144.3,144.0,139.6(d,J=13.1Hz),136.6,135.4(d,J=6.0Hz),135.2(d,J=6.1Hz),133.8,130.8,129.2(d,J=14.7Hz),128.8,128.6(d,J=9.9Hz),128.4(d,J=9.2Hz),127.9,127.0(d,J=6.7Hz),122.1,121.8,121.6,121.1,117.6,116.5,114.0,114.0,113.9,113.1,110.4,55.2,55.1,49.3.HRMS(MALDI)Calcd for C32H30N2P[M+H]+:505.2039;Found:505.2037.
实施例3
合成方法同配体1,白色固体,两步收率74%,熔点:60~62℃。
1H NMR(400MHz,CDCl3)δ8.50(d,J=4.9Hz,1H),7.57-7.51(m,1H),7.45-7.37(m,2H),7.34-7.28(m,4H),7.15(dd,J=7.8,2.8Hz,1H),7.11-7.05(m,4H),7.00(d,J=7.8Hz,2H),6.66(d,J=7.0Hz,1H),6.53(t,J=7.4Hz,1H),6.46(d,J=8.1Hz,1H),4.35(d,J=6.6Hz,1H),4.19(s,1H),1.21(s,18H),1.18(s,18H).31P NMR(162MHz,CDCl3)δ-11.11(s).13C NMR(101MHz,CDCl3)δ159.8,150.3(d,J=6.4Hz),150.1(d,J=6.6Hz),149.2,144.6,144.3(d,J=30.2Hz),140.1(d,J=13.8Hz),136.7,136.3(d,J=10.2Hz),133.9,131.0,130.7(d,J=4.8Hz),129.1,128.6,128.5,128.3(d,J=3.2Hz),128.1,127.7,127.4(d,J=6.9Hz),122.2(d,J=9.8Hz),121.7,121.0(d,J=3.6Hz),116.6,110.4,49.5,34.9,31.5(d,J=2.6Hz).HRMS(MALDI)Calcd for C40H53NP[M+H]+:669.4332;Found:669.4337.
实施例4
配体4的制备
在装有磁力搅拌子的干燥洁净的15mL Schlenk管中加入叔丁基硫基乙酸(75.6mg,0.45mmol),将体系置换为氩气氛围,加入1mL新蒸的二氯亚砜。油浴加热至80℃反应0.5小时,冷却至室温,减压脱除二氯亚砜,残余物用二氯甲烷(2mL)稀释后得到叔丁基硫基乙酰氯溶液。
在另一装有磁力搅拌子的干燥洁净的15mL Schlenk管中加入2′-二苯基膦基-2-胺基-1,1′-联苯13(106mg,0.3mmol),将体系置换为氩气氛围,先后加入二氯甲烷(2mL)和吡啶(119mg,1.5mmol),搅拌溶解。在冰水浴冷却下,向体系中滴加叔丁基乙酰氯的二氯甲烷溶液。滴毕,室温搅拌2小时,TLC检测反应完全。用饱和碳酸氢钠水溶液淬灭反应,乙酸乙酯萃取(5mL×3),有机相用饱和食盐水洗涤,无水硫酸钠干燥,静置。抽滤除去干燥剂,滤液用旋转蒸发仪脱除溶剂后得粗产品14。
在装有磁力搅拌子的干燥洁净的15mL Schlenk管中加入无水氯化铝(120mg,0.9mmol)和氢化铝锂(34mg,0.9mmol),将体系置换为氩气氛围,加入3mL无水乙醚,油浴加热至40℃反应0.5小时。将体系冷却至室温,用注射器向体系中滴加粗产品14的乙醚溶液(3mL)。滴毕,室温搅拌2小时,TLC检测原料反应完全。在冰水浴冷却下,向体系中滴加2mL水淬灭反应,分液,水相用乙醚萃取(5mL×3)。有机相用饱和食盐水洗涤,无水硫酸钠干燥,静置。抽滤除去干燥剂,滤液用旋转蒸发仪脱除溶剂。残余物经硅胶柱层析(石油醚/乙酸乙酯=10∶1)得到103mg白色固体4,两步收率73%,熔点:132~135℃。
1H NMR(400MHz,CDCl3)δ7.41(td,J=7.4,1.0Hz,1H),7.32-7.22(m,10H),7.20-7.10(m,4H),6.68(dd,J=7.4,1.3Hz,1H),6.62(d,J=8.1Hz,1H),6.55(t,J=7.3Hz,1H),3.69(t,J=4.9Hz,1H),3.21(td,J=13.0,6.7Hz,1H),3.09(td,J=12.4,6.9Hz,1H),2.60(t,J=7.0Hz,2H),1.22(s,9H).31P NMR(162MHz,CDCl3)δ-13.86(s).13C NMR(101MHz,CDCl3)δ144.8,144.6(d,J=31.2Hz),138.5(d,J=12.6Hz),137.7(d,J=12.9Hz),137.4(d,J=12.2Hz),134.2(s),134.0(d,J=4.7Hz),133.8(d,J=4.6Hz),130.9(d,J=3.1Hz),130.8,129.4,128.9,128.3(d,J=12.6Hz),128.3(d,J=14.1Hz),127.9,127.1(d,J=7.0Hz),116.4,110.1,43.5,42.2,31.0,28.1,27.0.HRMS(MALDI)Calcd for C30H33NPS[M+H]+:470.2066;Found:470.2064.
实施例5
配体5的制备
合成方法同配体4,白色固体,两步收率68%,熔点:122~124℃。
1H NMR(400MHz,CDCl3)δ7.42(t,J=6.9Hz,1H),7.34-7.13(m,16H),7.07(d,J=8.0Hz,2H),6.69(d,J=6.2Hz,1H),6.58-6.52(m,2H),3.66(t,J=6.0Hz,1H),3.25-3.06(m,2H),2.97-2.88(m,1H),2.86-2.78(m,1H),2.32(s,3H).31P NMR(162MHz,CDCl3)δ-13.87(s).13C NMR(101MHz,CDCl3)δ145.2,139.1(d,J=12.2Hz),138.3(d,J=13.6Hz),138.1,137.4,135.0,134.5(d,J=19.8Hz),131.7,131.6,131.5(d,J=5.1Hz),130.4,130.1,129.5,129.1,129.0,128.9,128.6,117.2,110.7,43.3,34.8,21.7.HRMS(MALDI)Calcd forC33H31NPS[M+H]+:504.1909;Found:504.1915.
实施例6
络合物6的制备
于氩气氛围的手套箱中,在装有磁力搅拌子的干燥洁净的15mL封管中加入1(46.7mg,0.105mmol)和RuCl2(DMSO)4(48mg,0.10mmol),加入2mL冻融脱气的无水甲苯,油浴控温120℃下搅拌反应16小时。将体系冷却至室温,将溶液转移至10mLSchlenk管中,高真空下脱除溶剂,残余物用乙醚(5mL×3)洗涤,抽滤,真空干燥,得黄色固体粉末61mg,产率:88%。
1H NMR(400MHz,CDCl3)δ10.01(d,J=5.7Hz,1H),7.68(s,2H),7.45-7.27(m,6H),7.21-7.12(m,5H),7.09-6.97(m,4H),6.88(t,J=8.5Hz,1H),6.77(t,J=7.5Hz,1H),6.67(t,J=7.5Hz,1H),6.50(d,J=7.6Hz,1H),6.41(d,J=7.6Hz,1H),5.05(dd,J=17.7,10.2Hz,1H),4.31(d,J=17.9Hz,1H),3.60(s,3H),2.49(s,3H).31P NMR(162MHz,CDCl3)δ39.52(s).13C NMR(101MHz,CDCl3)δ166.1,155.6,147.0,142.8(d,J=10.5Hz),137.9,136.8,136.4,134.7,134.5,134.3,133.7,132.5(d,J=3.9Hz),132.0(d,J=46.0Hz),131.0(d,J=6.8Hz),129.7,129.7,129.0,128.2,127.3,127.0(d,J=7.1Hz),125.3,125.1,124.1(d,J=2.2Hz),123.2(d,J=2.2Hz),123.1,121.5,119.1,60.9,49.0,45.6.HRMS(ESI)Calcd for C32H38ClNOPRuS2[M-Cl]+:659.0621;Found:659.0626.
实施例7
络合物7的制备
合成方法同络合物6,黄色固体,收率83%。
1H NMR(400MHz,CDCl3)δ7.67(t,J=8.3Hz,1H),7.53(t,J=7.4Hz,1H),7.45-7.33(m,5H),7.28-7.19(m,4H),7.12-7.02(m,4H),6.63(t,J=6.8Hz,1H),6.51(d,J=6.6Hz,1H),6.33(d,J=7.6Hz,1H),3.86-3.70(m,1H),3.64-3.50(m,1H),3.36(d,J=12.6Hz,1H),3.26(s,3H),3.06(d,J=14.2Hz,1H),2.86(s,3H),1.66(s,9H).31P NMR(162MHz,CDCl3)δ28.81(s).13C NMR(101MHz,CDCl3)δ147.4,140.4(d,J=11.7Hz),135.3(d,J=43.4Hz),134.5(d,J=41.0Hz),134.1(d,J=4.0Hz),132.4(d,J=6.9Hz),131.5(d,J=41.1Hz),130.4,129.6,128.0(d,J=9.0Hz),127.5,127.4(d,J=7.2Hz),127.2(d,J=9.8Hz),124.4,120.5,56.5,51.6,49.1,48.8,34.8,30.9.HRMS(ESI)Calcd for C32H38ClNOPRuS2[M-Cl]+:684.0859;Found:684.0853.
实施例8
络合物8的制备
于氩气氛围的手套箱中,在装有磁力搅拌子的干燥洁净的10mL封管中加入25a(46.7mg,0.105mmol)和RuHCl(CO)(PPh3)3(95mg,0.1mmol),加入5mL冻融脱气的无水四氢呋喃,用塞子封好后取出。体系用油浴控温至100℃搅拌反应6小时。将体系冷却至室温,将体系内黄色液体转移至10mL干燥洁净的Schlenk管中并在真空下脱除溶剂,残余物用乙醚(2mL)和正己烷(10mL)洗涤,于氩气氛围下抽滤,真空干燥,得白色固体粉末45mg,产率:73%。
1H NMR(400MHz,CD2Cl2)δ8.98(s,1H),7.99(s,2H),7.84(t,J=7.8Hz,1H),7.73-7.59(m,1H),7.56-7.12(m,14H),7.05(dd,J=17.8,8.9Hz,2H),6.78-6.59(m,3H),5.58(d,J=7.8Hz,1H),5.30(dd,J=16.8,8.4Hz,1H),4.34(d,J=16.8Hz,1H),-13.57(d,J=23.0Hz,1H).31P NMR(162MHz,CD2Cl2)δ59.60(s).13C NMR(101MHz,CD2Cl2)δ205.7(d,J=18.7Hz),162.1,155.5,153.0,150.4,141.1(d,J=12.0Hz),137.5,134.8(d,J=11.6Hz),133.3(d,J=6.8Hz),132.9(d,J=5.3Hz),131.6,131.0,130.4(d,J=41.3Hz),129.3,128.7(d,J=6.9Hz),128.6,128.5,127.9(d,J=10.5Hz),124.1,123.7,121.0,115.1,57.7(d,J=1.9Hz).HRMS(ESI)Calcd for C31H26RuN2OP[M-Cl]+:575.0821;Found:575.0816.
实施例9
络合物9的制备
合成方法同络合物8,白色固体,收率62%。
1H NMR(400MHz,CD2Cl2)δ8.98(s,1H),7.95(s,1H),7.83(t,J=7.7Hz,1H),7.62(t,J=7.3Hz,1H),7.46(d,J=7.7Hz,1H),7.41(t,J=7.5Hz,1H),7.36-7.24(m,4H),7.04(t,J=8.0Hz,2H),6.98(d,J=8.1Hz,2H),6.82-6.71(m,3H),6.67(t,J=8.7Hz,2H),5.54(d,J=8.2Hz,1H),5.29(dd,J=16.8,8.5Hz,1H),4.33(d,J=16.8Hz,1H),3.87(s,3H),3.79(s,3H),-13.67(d,J=23.0Hz,1H).31P NMR(162MHz,CD2Cl2)δ55.65(s).13C NMR(101MHz,CD2Cl2)δ203.7,162.1,153.0,150.2,137.4,136.1(d,J=13.3Hz),133.2(d,J=6.8Hz),132.8(d,J=5.8Hz),131.1(d,J=55.1Hz),129.2,128.6,128.5,126.1,125.6,124.0,123.7,120.9,119.2(d,J=6.0Hz),115.0,114.0,113.9,113.3(d,J=11.6Hz),57.7,55.6.HRMS(ESI)Calcd for C33H30RuN2O3P[M-Cl]+:635.1032;Found:635.1037.
实施例10
络合物10的制备
合成方法同络合物8,白色固体,收率68%。
1H NMR(400MHz,CD2Cl2)δ9.05(d,J=5.3Hz,1H),7.83(t,J=7.7Hz,1H),7.59(t,J=7.5Hz,1H),7.52-7.37(m,3H),7.37-7.22(m,5H),7.20-7.13(m,1H),7.06-6.95(m,2H),6.69(d,J=8.2Hz,1H),6.60(t,J=7.4Hz,1H),6.47(d,J=7.5Hz,1H),5.61(d,J=8.4Hz,1H),5.30(dd,J=16.9,8.5Hz,1H),4.34(d,J=17.0Hz,1H),3.72(t,J=6.2Hz,1H),1.30(s,18H),1.20(s,18H),-13.47(d,J=22.4Hz,1H).31P NMR(162MHz,CD2Cl2)δ61.53(s).13CNMR(101MHz,CD2Cl2)δ204.3(d,J=10.4Hz),176.3,162.2,153.2,150.6(d,J=9.2Hz),150.2,149.7(d,J=12.8Hz),141.0(d,J=11.3Hz),137.9,137.6,137.1,133.6,133.4,132.8,132.8(d,J=3.2Hz),132.7,131.2,130.5,129.1,128.3(d,J=6.7Hz),124.1,123.9,123.8(d,J=1.6Hz),123.4,120.8,115.2,57.7(d,J=2.8Hz),35.4,35.0,31.6,31.5.HRMS(ESI)Calcd for C47H59RuN2OP[M-Cl]+:800.3404;Found:800.3403.
实施例11
络合物11的制备
合成方法同络合物8,黄色固体,收率43%。
1H NMR(400MHz,CD2Cl2)δ7.95(t,J=7.6Hz,1H),7.82(t,J=7.7Hz,2H),7.73-7.27(m,6H),7.25-6.91(m,4H),6.72(dd,J=17.3,8.2Hz,4H),6.64(d,J=7.5Hz,1H),4.35-4.30(m,1H),3.23(m,1H),3.11(m,1H),2.97-2.92(m,1H),2.88-2.84(m,1H),1.19(s,9H),-13.67(d,J=23.0Hz,1H).31P NMR(162MHz,CD2Cl2)δ58.73(s).
实施例12
络合物12的制备
合成方法同络合物8,黄色固体,收率56%。
1H NMR(400MHz,CD2Cl2)δ8.04(d,J=7.8Hz,1H),7.92-7.84(m,1H),7.75-7.67(m,1H),7.55(dt,J=16.5,8.0Hz,3H),7.44-6.95(m,11H),6.83(ddd,J=29.4,14.4,7.8Hz,3H),6.53-6.47(m,1H),6.36(d,J=7.5Hz,1H),4.85-4.78(m,1H),3.82-3.72(m,1H),3.68(t,J=5.8Hz,1H),3.20-3.13(m,1H),3.08(d,J=15.9Hz,1H),2.43(s,3H),-13.58(d,J=19.6Hz,1H).31P NMR(162MHz,CD2Cl2)δ56.38(s).
实施例13
以γ-戊内酯为例阐述酯类化合物催化氢化反应的操作:
在手套箱中称取联吡啶四齿配体钌络合物6(2.0mg,3.0μmol)和甲醇钠(17mg,0.3mmol)于装有磁力搅拌子的玻璃反应内管中,用注射器向其中加入冻融脱气的预先配制的γ-戊内酯(300mg,3.0mmol)的四氢呋喃(3.0mL)溶液,搅拌均匀,迅速放于高压釜中,置换为氩气氛围。用氢气置换高压釜中的气体五次,最后调节氢气压力为5MPa,80℃搅拌反应16小时至压力表不再变化,缓慢释放出高压釜中的氢气,加入正十三烷作为内标,取少量样品经短硅胶柱过滤后用气相色谱测定1,4-戊二醇的收率为>99%。
使用合成制备的固体联苯型三齿配体钌络合物7为催化剂催化氢化γ-戊内酯反应12小时后,1,4-戊二醇收率为35%;使用合成制备的固体联苯型三齿配体钌络合物8为催化剂催化氢化γ-戊内酯反应1.5小时后,1,4-戊二醇收率为>99%;使用合成制备的固体联苯型三齿配体钌络合物9为催化剂催化氢化γ-戊内酯反应1.2小时后,1,4-戊二醇收率为>99%;使用合成制备的固体联苯型三齿配体钌络合物10为催化剂催化氢化γ-戊内酯反应2小时后,1,4-戊二醇收率为>99%;使用合成制备的固体联苯型三齿配体钌络合物11为催化剂催化氢化γ-戊内酯反应12小时后,1,4-戊二醇收率为12%;使用合成制备的固体联苯型三齿配体钌络合物12为催化剂催化氢化γ-戊内酯反应12小时后,1,4-戊二醇收率为3%。
气相色谱分析条件为:Agilent HP-INNOWAX色谱柱(30m×0.32mm×0.25μm),FID检测器,进样口温度为230℃,检测器温度为250℃,载气为氮气,流速恒定为1.0mL/min,程序升温:初始温度为50℃,以10℃/min的升温速率升至250℃,在该温度下保持10分钟。正十三烷、γ-戊内酯、1,4-戊二醇的保留时间分别为6.39min、10.82min、13.61min。
实施例9
以γ-戊内酯为底物使用合成制备的联吡啶四齿配体钌络合物8优化比较催化氢化反应的实验条件,不同催化剂、溶剂、碱和氢气压力等实验条件的反应结果见表1。
表1γ-戊内酯氢化反应实验条件的比较a
a反应条件:S/C=1000,3.0mmolγ-戊内酯,3.0μmol 8,3.0mLTHF,25℃。b由气谱测定,括号内为分离收率,在所有反应中均只观察到1,4-戊二醇和未反应的γ-戊内酯存在。cS/C=10,000,300mmolγ-戊内酯,3.0μmol 8,3.0mmol NaOMe。dS/C=100,000,300mmolγ-戊内酯,0.3μmol 8,30mL THF,30mmol NaOMe。
实施例10
使用合成制备的联吡啶四齿配体钌络合物5催化氢化其它酯类化合物的氢化反应结果见表2:
表2其它酯类化合物的氢化反应a
a反应条件:3mmol III,3μmol 8,0.3mmol NaOMe,3.0mL THF。b转化率由气相色谱测定,加入正十三烷为内标,在所有反应中均只观察到III和IV-a,括号内为分离收率。c30mmol III-a,3μmol 8,3mmol NaOMe,15.0mL THF(S/C=10,000)。d300mmol III-j,3μmol8,30mmol NaOMe(S/C=100,000)。e产物IV-a-o为1,4-戊二醇。fIV-a-p是双键也被还原的产物。
通过上述实施例证明了联苯型三齿配体合成方便,其相应的钌络合物制备简单,稳定性好,并且在酯类化合氢化反应中表现出优异的催化活性,催化剂用量小,反应条件温和,反应的选择性好,显示出了很好的工业应用价值。
Claims (10)
1.一种联苯型三齿配体,其特征在于它具有如I所示的结构式:
其中,配位基团L1选自:PR1R2,配位基团L2选自:吡啶、CH2SR;
R、R1和R2独立地选自:C1~C8烷基、C3~C8环烷基、苯基、取代的苯基、1-萘基、2-萘基、杂芳基、苄基;所述的取代的苯基上的取代基为C1~C8烷基、C3~C8环烷基、苯基、烷氧基以及卤素,取代基数量为1~5;所述的杂芳基为呋喃基、噻吩基或吡啶基;R1、R2相同,或不同;或R1、R2并为C3~C8脂肪环或芳香环;
X1、X2独立地选自:H、C1~C8烷基、C3~C8环烷基、苯基、取代的苯基、1-萘基、2-萘基、杂芳基、苄基、卤素;所述的取代的苯基上的取代基为C1~C8烷基、C3~C8环烷基、苯基、烷氧基以及卤素,取代基数量为1~5;所述的杂芳基为呋喃基、噻吩基或吡啶基;m=0~3,n=0~3;当m≥2时,两个相邻的X1并为C3~C8脂肪环或芳香环;当n≥2时,两个相邻的X2并为C3~C8脂肪环或芳香环;X1、X2相同,或不同。
2.按照权利要求1所述的联苯型三齿配体,其特征在于所述的C1~C8烷基为甲基、乙基、正丙基、异丙基、正丁基、叔丁基;所述的C3~C8环烷基为环丙基、环丁基、环戊基、环己基;所述的烷氧基为甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、叔丁氧基。
3.按照权利要求1所述的联苯型三齿配体,其特征在于所述的联苯型三齿配体为结构式1-5所示:
4.一种由权利要求1所述的联苯型三齿配体制备的联苯型三齿配体钌络合物,其特征在于它具有如II所示的结构式:
其中,L1、L2、X1、X2、m、n的定义与通式I所述相同;Y,Z为H、Cl、Br、I、ClO4、PF6、BPh4、B(C6F5)4、BF4、BH4、OCOR、OCOCF3、OSO2R、OSO2CF3、CN、OR、NR2、SR、R2S(O)、CO、PR3;R为H、C1~C8烷基、C3~C8环烷基、苯基、取代的苯基、1-萘基、2-萘基、杂芳基、苄基;所述的取代的苯基上的取代基为C1~C8烷基、C3~C8环烷基、苯基、烷氧基以及卤素,取代基数量为1~5;所述的杂芳基为呋喃基、噻吩基或吡啶基;X,Y,Z相同或不同。
5.根据权利要求4所述的联苯型三齿配体钌络合物,其特征在于所述的X,Y,Z为不同的Cl、CO、H或二甲基亚砜。
6.根据权利要求4所述的联苯型三齿配体钌络合物,其特征在于所述的联苯型三齿配体钌络合物为结构式6-12所示:
7.权利要求6所述的联苯型三齿配体钌络合物的制备方法,其特征在于包括如下方法:
合成制备:在二氯甲烷、四氢呋喃、甲苯、N,N-二甲基甲酰胺、二甲亚砜有机溶剂中,金属钌前体和相对于钌原子物质的量1.0~1.5倍量的所述联苯型三齿配体,在25~120℃反应4~16小时,溶液旋转蒸发至原体积1/10;将浓缩的溶液在搅拌下加入乙醚或正己烷,析出白色或者黄色固体,真空抽滤,用乙醚或正己烷洗涤滤饼,滤饼真空干燥后得到固体联苯型三齿配体钌络合物;
所述的金属钌前体是RuCl3·nH2O、[RuCl2(CO)3]2、[Ru(cod)Cl2]n、[Ru(nbd)Cl2]n、[RuCl2(benzene)]2、[RuBr2(benzene)]2、[RuI2(benzene)]2、[RuCl2(η6-p-cymene)]2、[RuBr2(η6-p-cymene)]2、[RuI2(η6-p-cymene)]2、[RuCl2(mesitylene)]2、[RuBr2(mesitylene)]2、[RuI2(mesitylene)]2、RuCl2(PPh3)3,、RuBr2(PPh3)3、RuI2(PPh3)3、RuCl2(DMSO)4、Ru(H)Cl(CO)(PPh3)3,其中:cod=1,5-环辛二烯,nbd=2,5-降冰片二烯,DMSO=二甲亚砜。
8.权利要求4所述的联苯型三齿配体钌络合物的应用,其特征在于它作为催化剂用于酯类化合物催化氢化合成醇类化合物的反应中,所述的酯类化合物如通式III所示:
其中,Ra、Rb选自C1~C30烷基、C3~C30环烷基、C2~C30烯基、C3~C30环烯基、芳基,这些基团中含有任意不影响氢化反应的取代基,Ra、Rb相同或不同;或Ra、Rb相连即形成环状的C4~C30的内酯,内酯环上含有任意不影响氢化反应的取代基,内酯环上合适位置的碳原子可被O、N、S杂原子取代,内酯环是单环或多环;所述的内酯是饱和内酯或不饱和内酯;
所述的醇类化合物如通式IV-a、IV-b所示:
Ra、Rb的定义与通式III中所述相同;当Ra、Rb未相连时所述的醇类化合物如IV-a、IV-b所示;当Ra、Rb相连时所述的醇类化合物是相应内酯还原后所得的二元醇;当氢化所用的酯类化合物中含有多个酯基时,所得的醇类化合物为相应的多元醇。
9.根据权利要求8所述的联苯型三齿配体钌络合物的应用,其特征在于所述的酯类化合物为:苯甲酸甲酯、乙酸乙酯、乙二醇碳酸酯、乙酰丙酸甲酯、琥珀酸二甲酯、γ-丁内酯、γ-戊内酯、α-甲基-γ-丁内酯、乙醇酸甲酯、乳酸甲酯、甲氧基乙酸甲酯、月桂酸甲酯、硬脂酸甲酯、三月桂酸甘油酯、三硬脂酸甘油酯、草酸二甲酯、1,2-苯二甲酸甲酯、1,3-苯二甲酸甲酯、己酸甲酯、己酸己酯。
10.根据权利要求8所述的联苯型三齿配体钌络合物的应用,其特征在于对酯类化合物的催化氢化应用的方法包括如下步骤:
在氩气或氮气保护下,将催化剂即联苯型三齿配体钌络合物和碱加入反应釜内管中,加入底物溶于相应溶剂的溶液,拧紧反应釜并用氢气小心置换3~5次,调节氢气压力至所需压力后,在合适温度下搅拌反应至压力不再变化,将反应釜恢复室温,缓慢释放剩余氢气;产物通过柱层析、蒸馏常用有机化合物纯化方法进行分离提纯;
催化剂用量为底物物质的量的0.001~0.1mol%,碱用量为底物物质的量的1~10mol%,氢气压力3~10MPa,反应温度为60~100℃,反应时间为1~64小时;
所用溶剂为四氢呋喃、乙醚、2-甲基四氢呋喃、甲醇、乙醇、异丙醇、甲苯有机溶剂中的一种或其中几种的混合溶剂;所用碱的为甲醇钠、乙醇钠、异丙醇钠、叔丁醇钠、甲醇钾、乙醇钾、异丙醇钾、叔丁醇钾;碱的用量为酯类化合物物质的量的1~10mol%。
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