CN102950025B - Asymmetric hydrogenation catalyst of imine and its use - Google Patents
Asymmetric hydrogenation catalyst of imine and its use Download PDFInfo
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- CN102950025B CN102950025B CN201110242308.3A CN201110242308A CN102950025B CN 102950025 B CN102950025 B CN 102950025B CN 201110242308 A CN201110242308 A CN 201110242308A CN 102950025 B CN102950025 B CN 102950025B
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- Prior art keywords
- imine
- alkyl
- catalyst
- formula
- phenyl
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- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 150000002466 imines Chemical class 0.000 title claims abstract description 30
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 title claims abstract description 14
- 239000003446 ligand Substances 0.000 claims abstract description 26
- 150000001412 amines Chemical class 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 7
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 4
- ORBBTCHHNMWMCP-UHFFFAOYSA-K cycloocta-1,5-diene trichloroiridium Chemical compound [Ir](Cl)(Cl)Cl.C1=CCCC=CCC1 ORBBTCHHNMWMCP-UHFFFAOYSA-K 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 2
- 239000000575 pesticide Substances 0.000 abstract description 7
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 abstract 1
- WVQBLGZPHOPPFO-LBPRGKRZSA-N (S)-metolachlor Chemical compound CCC1=CC=CC(C)=C1N([C@@H](C)COC)C(=O)CCl WVQBLGZPHOPPFO-LBPRGKRZSA-N 0.000 abstract 1
- 239000005617 S-Metolachlor Substances 0.000 abstract 1
- GQENPXQJRUSMDY-UHFFFAOYSA-N [Ir+].ClC1=CCCC=CCC1 Chemical group [Ir+].ClC1=CCCC=CCC1 GQENPXQJRUSMDY-UHFFFAOYSA-N 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 239000002994 raw material Substances 0.000 description 11
- 238000004817 gas chromatography Methods 0.000 description 9
- 238000004128 high performance liquid chromatography Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000000543 intermediate Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 7
- 125000001453 quaternary ammonium group Chemical group 0.000 description 7
- 229940107816 ammonium iodide Drugs 0.000 description 6
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 6
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 4
- JJVKJJNCIILLRP-UHFFFAOYSA-N 2-ethyl-6-methylaniline Chemical compound CCC1=CC=CC(C)=C1N JJVKJJNCIILLRP-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- -1 aldehyde compound Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- CUZLJOLBIRPEFB-UHFFFAOYSA-N 1-methoxypropan-2-one Chemical compound COCC(C)=O CUZLJOLBIRPEFB-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000011982 enantioselective catalyst Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 150000008365 aromatic ketones Chemical class 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical group OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IIQIBCQCZQPBFE-UHFFFAOYSA-N [Li]CCCC.CN(C)CCN(C)C Chemical compound [Li]CCCC.CN(C)CCN(C)C IIQIBCQCZQPBFE-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- LRRJQNMXIDXNIM-UHFFFAOYSA-M benzyl(trimethyl)azanium;iodide Chemical compound [I-].C[N+](C)(C)CC1=CC=CC=C1 LRRJQNMXIDXNIM-UHFFFAOYSA-M 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910001505 inorganic iodide Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002496 iodine Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
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CN201110242308.3A CN102950025B (en) | 2011-08-23 | 2011-08-23 | Asymmetric hydrogenation catalyst of imine and its use |
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CN201110242308.3A CN102950025B (en) | 2011-08-23 | 2011-08-23 | Asymmetric hydrogenation catalyst of imine and its use |
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CN102950025A CN102950025A (en) | 2013-03-06 |
CN102950025B true CN102950025B (en) | 2014-09-10 |
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CN201110242308.3A Expired - Fee Related CN102950025B (en) | 2011-08-23 | 2011-08-23 | Asymmetric hydrogenation catalyst of imine and its use |
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CN106810554B (en) * | 2017-01-14 | 2019-02-15 | 山东罗欣药业集团恒欣药业有限公司 | A kind of preparation method of Tadalafei compound |
CN110551037B (en) * | 2018-05-31 | 2021-11-09 | 中国科学院大连化学物理研究所 | Method for catalyzing asymmetric hydrogenation of imine by iridium/chiral diphosphine system |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0646590A1 (en) * | 1993-10-01 | 1995-04-05 | Ciba-Geigy Ag | Ferrocenyldiphosphines substituted with fluoroalkyl groups as ligands for homogeneous catalysis |
US5466844A (en) * | 1993-02-26 | 1995-11-14 | Ciba-Geigy Corporation | Ferrocene diphosphines as ligands for homogeneous catalysts |
CN1139930A (en) * | 1994-02-02 | 1997-01-08 | 希巴-盖吉股份公司 | Hydrogenation catalyst, process for the preparation thereof and hydrogenation process |
EP0691949B1 (en) * | 1994-02-02 | 1998-10-14 | Novartis AG | Process for the hydrogenation of imines |
CN101857612A (en) * | 2010-06-11 | 2010-10-13 | 南京工业大学 | Chiral diphosphine ligand, iridium composite catalyst thereof, preparation method and application of chiral diphosphine ligand in asymmetric hydrogenation synthesis of -metolachlor |
-
2011
- 2011-08-23 CN CN201110242308.3A patent/CN102950025B/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5466844A (en) * | 1993-02-26 | 1995-11-14 | Ciba-Geigy Corporation | Ferrocene diphosphines as ligands for homogeneous catalysts |
EP0646590A1 (en) * | 1993-10-01 | 1995-04-05 | Ciba-Geigy Ag | Ferrocenyldiphosphines substituted with fluoroalkyl groups as ligands for homogeneous catalysis |
CN1139930A (en) * | 1994-02-02 | 1997-01-08 | 希巴-盖吉股份公司 | Hydrogenation catalyst, process for the preparation thereof and hydrogenation process |
EP0691949B1 (en) * | 1994-02-02 | 1998-10-14 | Novartis AG | Process for the hydrogenation of imines |
CN101857612A (en) * | 2010-06-11 | 2010-10-13 | 南京工业大学 | Chiral diphosphine ligand, iridium composite catalyst thereof, preparation method and application of chiral diphosphine ligand in asymmetric hydrogenation synthesis of -metolachlor |
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CN102950025A (en) | 2013-03-06 |
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Effective date of registration: 20160119 Address after: 110021 Liaodong Road, Tiexi District, Liaoning, No. 8-1, No. Patentee after: SHENYANG SINOCHEM AGROCHEMICALS R&D Co.,Ltd. Address before: 100031 Beijing, Xicheng District, the door of the revitalization of the main street, No. 28 Patentee before: SINOCHEM Corp. Patentee before: SHENYANG RESEARCH INSTITUTE OF CHEMICAL INDUSTRY Co.,Ltd. |
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Effective date of registration: 20180619 Address after: 200120 China (Shanghai) free trade pilot area No. 581 Shen Kuo Road Patentee after: SHANGHAI ZHONGHUA TECHNOLOGY Co.,Ltd. Address before: 110021 Shenyang Liaodong Road, Tiexi District, Shenyang, Liaoning 8-1 Patentee before: SHENYANG SINOCHEM AGROCHEMICALS R&D Co.,Ltd. |
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