CN1980883B - Method for the production of optically active alkyl succinic acid monoalkyl esters - Google Patents
Method for the production of optically active alkyl succinic acid monoalkyl esters Download PDFInfo
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- CN1980883B CN1980883B CN2005800228341A CN200580022834A CN1980883B CN 1980883 B CN1980883 B CN 1980883B CN 2005800228341 A CN2005800228341 A CN 2005800228341A CN 200580022834 A CN200580022834 A CN 200580022834A CN 1980883 B CN1980883 B CN 1980883B
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- Prior art keywords
- hydrogenation
- alkyl
- catalyzer
- succinic acid
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- -1 alkyl succinic acid Chemical compound 0.000 title claims abstract description 15
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 239000001384 succinic acid Substances 0.000 title claims abstract description 10
- 150000002148 esters Chemical class 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 title claims description 37
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 238000005984 hydrogenation reaction Methods 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000004437 phosphorous atom Chemical group 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- GWLJTAJEHRYMCA-UHFFFAOYSA-N phospholane Chemical group C1CCPC1 GWLJTAJEHRYMCA-UHFFFAOYSA-N 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims 4
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 239000002244 precipitate Substances 0.000 claims 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 abstract description 6
- 125000002877 alkyl aryl group Chemical group 0.000 abstract description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000010948 rhodium Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- QEZMQNIFDRNSJZ-UHFFFAOYSA-N 4-methoxy-3-methyl-4-oxobutanoic acid Chemical compound COC(=O)C(C)CC(O)=O QEZMQNIFDRNSJZ-UHFFFAOYSA-N 0.000 description 4
- 229910020366 ClO 4 Inorganic materials 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910018286 SbF 6 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- UVQYBUYGFBXQGO-SCSAIBSYSA-N (2r)-4-methoxy-2-methyl-4-oxobutanoic acid Chemical compound COC(=O)C[C@@H](C)C(O)=O UVQYBUYGFBXQGO-SCSAIBSYSA-N 0.000 description 2
- KBFJHOCTSIMQKL-UHFFFAOYSA-N 3-methoxycarbonylbut-3-enoic acid Chemical compound COC(=O)C(=C)CC(O)=O KBFJHOCTSIMQKL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 229910021115 PF 6 Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- LYXHWHHENVLYCN-QMDOQEJBSA-N (1z,5z)-cycloocta-1,5-diene;rhodium;tetrafluoroborate Chemical compound [Rh].F[B-](F)(F)F.C\1C\C=C/CC\C=C/1.C\1C\C=C/CC\C=C/1 LYXHWHHENVLYCN-QMDOQEJBSA-N 0.000 description 1
- UVQYBUYGFBXQGO-BYPYZUCNSA-N (2s)-4-methoxy-2-methyl-4-oxobutanoic acid Chemical compound COC(=O)C[C@H](C)C(O)=O UVQYBUYGFBXQGO-BYPYZUCNSA-N 0.000 description 1
- WXUAQHNMJWJLTG-GSVOUGTGSA-N (R)-methylsuccinic acid Chemical compound OC(=O)[C@H](C)CC(O)=O WXUAQHNMJWJLTG-GSVOUGTGSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 238000011914 asymmetric synthesis Methods 0.000 description 1
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical class [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001400 nonyl 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])C([H])([H])[H] 0.000 description 1
- 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 1
- 239000012041 precatalyst Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical class [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- 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
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2419—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member
- B01J31/2428—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member with more than one complexing phosphine-P atom
- B01J31/2433—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- 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
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2419—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/827—Iridium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/828—Platinum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for producing optically active alkyl succinic acid monoalkyl esters of formula (I), wherein D and E independently represent H, C1-C10 alkyl, and R represents C1-C10 aryl or alkylaryl.
Description
The present invention relates to a kind of novel method for preparing optically active alkyl succinic acid monoalkyl esters.
Prior art
Up to now, can't obtain a kind of direct unsaturated precursor by them directly optionally forms III type system and optically active enantiomorph thereof by asymmetric hydrogenation path satisfactorily.
This can be by for example confirming that by methylene-succinic acid monomethyl ester 3 preparation (2R)-methylsuccinic acid 4-methyl ester 4 wherein methylene-succinic acid monomethyl ester 3 can easily obtain with low cost.
K.Achiwa, Y.Ohga, Y.Itaka, Tetrahedron Lett.1978,19,4683 in methyl alcohol, obtained the to have 60% enantiomeric excess compound 4 of (=ee=[enantiomorph 1 content-enantiomorph 2 content]/[enantiomorph 1 content+enantiomorph 2 content]).
W.C.Christopfel, B.D.Vineyard, J.Am.Chem.Soc.1979,101,4406 have obtained to have the compound 4 of 55%ee in methyl alcohol.
S.Saito, Y.Nakamura, Y.Morita, Chem.Pharm.Bull.1985,33,5284 have obtained to have the compound 4 of 90%ee in benzene/MeOH 1/4.
H.Kawano, Y.Ishii, T.Ikariya, M.Saburi, S.Yoshikawa, TetrahedronLett.1987,28,1905 have obtained to have the compound 4 of 60%ee in toluene/THF.
D.Carmichael, H.Doucet, J.M.Brown, Chem.Commun.1999,261 H.Kawano, T.Ikariya, Y.Ishii, M.Saburi, S.Yoshikawa et al., J.Chem.Soc.Perkin Trans.1 1989,1571 have obtained to have the compound 4 of 94%ee in methyl alcohol.
U.Berens, M.Burk, (WO 00/27855 for A.Gerlach; EP 1 127 061 B1) in methyl alcohol, obtained to have the compound 4 of 95%ee.
Therefore, under the situation of not having additional enriching step, the optical purity that aforesaid method reaches can not satisfy the requirement of activeconstituents aspect, and requirement in most cases is enantiomeric excess 〉=98%ee.
Other method that can reach higher optical purity is used a large amount of catalyzer, just low substrate/catalyst ratio (s/c), and this is uneconomic for industrial production; Perhaps selected reaction conditions (particularly solvent) is had in mind or is in-problem for the reason of Occupational safety from environmental.
M.Ostermeier, B.Brunner, C.Korff, G.Helmchen, Eur.J.Org.Chem.2003,3453 obtain to have the compound 4 of 97.3%ee with 200/1 s/c ratio in methylene dichloride, at C
6H
5CF
3In equally reached 98.3%ee with 200/1 s/c ratio.In ethylene dichloride, the s/c ratio with 1000/1 reaches purity 99.3%ee.
For the above reasons, all these methods all are not suitable on technical scale by directly synthesizing optically-active succsinic acid alkyl ester in one step of alkene precursor that obtains with low-cost and easy-to.
Goal of the invention
The purpose of this invention is to provide a kind of novel method for preparing optically active alkyl succinic acid monoalkyl esters, this method is used a spot of catalyzer (s/c 〉=20,000/1), have simultaneously with the reaction conditions of environmental harmony, completely reaction conversion ratio and high optical yield (〉=98%ee), therefore can carry out efficient, environmentally acceptable, effectively industry is synthetic for cost.
Summary of the invention
We have found that the method for a kind of preparation formula (I) optically active alkyl succinic acid monoalkyl esters,
Wherein D and E are H, C independently of one another
1-C
10Alkyl,
R is C
1-C
10Alkyl, aryl or alkylaryl,
This method in the presence of the catalyzer that comprises formula (L) phospholane part (phospholane ligand),
(L)
Wherein:
R
1And R
2Be C independently of one another
1-C
6Alkyl, aryl, alkylaryl,
R
1Be hydrogen in addition,
A is R
1Or
Condition is B=has 1-5 carbon atom between two P atoms connection base (Iinker) or Cp-Fe-Cp,
Enantioselectivity ground hydrogenation of formula (II) compound:
Wherein D, E and R have meaning mentioned above.
Formula (I) compound is the optically-active compound that is used for representing a kind of enantiomorph (R or S) in all cases.
Enantioselective hydrogenation is used to refer to following hydrogenation hereinafter: this hydrogenation can not obtain two kinds of enantiomorphs of same degree, and wherein a kind of enantiomorph (R or S) forms with high purity, the particularly purity with enantiomeric excess 98%, 99%, 99.5%.
The initial compounds of formula (II) can by document know and can be easily by the traditional method preparation (for D=E=H; R=Me, referring to for example, A.R.Devi, S.Rajaram, Ind.J.Chem.2000,39B, 294-296 or R.C.Anand, V.A.Milhotra, J.Chem.Res. (S) 1999,378-379 or R.N.Ram, I.Charles, Tetrahedron 1997,53,7335-7340).Preferred initial compounds (II) is those wherein D and E compounds of having following meaning independently of one another: H, methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, wherein said alkyl comprise the not isomer of branching and branching.Particularly preferred initial compounds is that wherein D and E are those of H and methyl, and especially wherein D and E are that H or D and E are those of methyl.Further preferred initial compounds (II) is that wherein D is that H and E are those of butyl.
Radicals R can be C
1-C
10Alkyl, each H atom in the wherein said alkyl can so that by other group such as OH, NH
2, NO
2, CN, F, Cl, Br, I replace.In addition, R can also be aryl such as phenyl, naphthyl; With alkylaryl such as benzyl, aryl wherein can also and then be substituted.Preferred R is methyl, ethyl, propyl group, sec.-propyl and the tertiary butyl.R is preferably methyl especially.
Described catalyzer comprises the atoms metal that is selected from Pd, Pt, Ru, Rh, Ni, Ir.Particularly preferred catalyzer has Rh, Ru or the Ir as atoms metal, and the Rh catalyzer is particularly suitable for the inventive method.
The source metal that can be preferred for preparing described catalyzer is for example Pd of precursor
2(DBA)
3, Pd (Oac)
2, [Rh (COD) Cl]
2, [Rh (COD)
2]] X, Rh (acac) is (CO)
2, RuCl
2(COD), Ru (COD) (methylallyl)
2, Ru (Ar) Cl
2, the aryl that Ar=does not replace and replaces, [Ir (COD) Cl]
2, [Ir (COD)
2] X, Ni (allyl group) X.Also preferably use NBD (=norbornadiene) replaced C OD (=1, the 5-cyclooctadiene).
X can be that those skilled in the art are known and can be used for any negatively charged ion of asymmetric synthesis in these cases.The example of X is for example Cl of halogen
-, Br
-, I
-, BF
4 -, ClO
4 -, SbF
6 -, PF
6 -, CF
3SO
3 -, BAr
4 -X is BF preferably
4 -, CF
3SO
3 -, SbF
6 -, ClO
4 -, BF particularly
4 -And CF
3SO
3 -
The catalyzer of the inventive method comprises the phospholane part of one or more formulas (L) in addition.Preferred substituted R
1And R
2Be H, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, benzyl.R
1=H and R
2The substituting group combination of=methyl is particularly preferred.
Two R wherein further preferably in addition
1Form the R of bridge
1Group, for example isopropylidene or benzylidene.
Under the situation of bisphospholane (diphospholanes), preferably following formula represent those.
The basic B of particularly preferred connection is n=1 or 2 or those of m=0 wherein.
Particularly preferred ligand L is that wherein A represents another one phospholane residue and is connected those of basic B, and wherein B can represent the bridge of two carbon atoms of the 1-5 between the phosphorus atom.1-5 carbon atom between described two phosphorus atom also do not mean that B comprises 5 carbon atoms at most, but the direct connection between two phosphorus atom comprises and is no more than 5 carbon atoms.B can be a phenyl ring for example, and condition is that two phosphorus atom are connected on the phenyl ring in contraposition.
But connecting basic B can also be ferrocene type compound, and it is by replacing or unsubstituted and form with the cyclopentadienyl (Cp) that sandwich form (Cp-Fe-Cp) comprises the Fe atom, and wherein the P Atom Bonding is to the Cp base.
Particularly preferred ligand L is:
The present invention not only comprises the enantiomorph of being represented by these structural formulas, but also comprises their optically active enantiomorph.
About the Rophos Preparation of catalysts, with reference to EP 0889048, it is for reference to quote this patent at this.
Part-metal complexes can be by comprising unstable part ([RuCl for example
2(COD)]
n, [Rh (COD)
2] BF
4, [Rh (COD)
2] CF
3SO
3, Rh (COD)
2ClO
4, [Ir (COD) Cl]
2, right-cymene ruthenium chloride dimer) rhodium, iridium, ruthenium, palladium, platinum, nickel complex reaction prepare with known manner synthesis catalytic labile coordination compound.But NBD also replaced C OD is used to prepare title complex, has good result.
As known to the those skilled in the art, title complex (=preformed catalyst precatalyst) can produce before using and separate, in time use then, or before actual hydrogenation generation (stating as follows) on the spot in reaction vessel.
Suitable solvent is the known solvents that are useful on asymmetric hydrogenation of those skilled in the art.Preferred solvent is a lower alkyl alcohol, for example methyl alcohol, ethanol, Virahol and toluene, THF, ethyl acetate.In the methods of the invention, methyl alcohol is preferably used as solvent especially.
Hydrogenation of the present invention is carried out under-20 ℃ to 150 ℃ usually, and preferred 0-100 ℃, preferred 10-80 ℃ especially.
The inventive method uses in all cases 〉=20,000/1 substrate/catalyst ratio (s/c), and result acquisition 〉=98%ee.Even the s/c ratio with 110,000/1 has also reached 98%ee.
The use of catalyzer can further be simplified by suitable stagnant catalyst.
For method for hydrogenation of the present invention, hydrogen pressure can change in the wide region of 0.1 crust-300 crust.In the pressure range of 1-200 crust, preferred 1-100 crust, obtain extraordinary result.
Reaction mixture utilizes the known step process of those skilled in the art.Product can for example be converted into carboxylate salt, precipitation and and then from catalyzer, remove, discharge again subsequently; Alternative possible method is by absorption that catalyzer is fixing in bed, can easily carry out chromatogram like this and purify.Can also catalyzer be shifted out from product by distillation.
By the product buffering be carboxylate salt and from reaction mixture, precipitating simply enantiomeric excess can be brought up to>99.5%.To this suitable alkali is known all alkali of those skilled in the art, and wherein preferred amines and guanidine are as neutral alkali (neutral bases), and carboxylate salt, carbonate, oxyhydroxide, oxide compound are as metal base.Particularly preferred metal base is corresponding lithium compound.
Other is preferred embodiment described in appended claims and experimental section.
Experimental section
Embodiment 1
Preparation optically-active methylsuccinic acid methyl ester (s/c 20,000/1)
Under shielding gas with (RophosARhCOD) CF of 133mg (0.182mmol)
3SO
3(=preformed catalyst) is introduced in 4 liters of 21ml methyl alcohol in (enamel) Pfaudler autoclave, and adds 526g (3.65mol) the 2-methene succinic acid 4-mono-methyl (=substrate) that is dissolved in the 704ml methyl alcohol.Cling under the hydrogen at 40 ℃ and 5 then and carry out hydrogenation.Substrate conversion after 4 hours, finish (
1H-NMR, 500MHz).Mapping by gas Chromatographic Determination product (2R)-methylsuccinic acid 4-mono-methyl is excessive>98% (source: BGB-Analytik, column type: BGB-174, length 30m, internal diameter: 0.25ml, film thickness: 0.25 μ m, carrier gas: helium, inlet pressure: 2.35 crust, temperature: 135 ℃, heating rate: 1.2 ℃/min, the retention time of R enantiomorph: 23.3 minutes, the retention time of S enantiomorph: 22.6 minutes).The s/c ratio is 20,000: 1.
Embodiment 2
Preparation optically-active methylsuccinic acid methyl ester (s/c 40,000/1)
With 40,000: catalyzer/substrate ratio s/c of 1 carries out the reaction that embodiment 1 describes.Substrate conversion was finished after 4 hours.The enantiomeric excess of product>98%.
Embodiment 3
Preparation optically-active methylsuccinic acid methyl ester (s/c 110,000/1)
Under shielding gas, 5.73g (39.8mmol) 2-methene succinic acid-4-mono-methyl is introduced in the 12ml methyl alcohol in the 50ml glass autoclave, and adds 6.6mg (RophosARhCOD) CF of 0.12ml
3SO
3(=preformed catalyst) solution (0.00036mmol preformed catalyst) in 3ml methyl alcohol.Cling under the hydrogen at 60 ℃, 5 then and carry out hydrogenation.The conversion of precursor was finished after 16 hours.The enantiomeric excess of this product is 98%.
Embodiment 4
Preparation optically-active methylsuccinic acid methyl ester then forms lithium salts on technical scale
Under shielding gas, 75kg methene succinic acid 4-mono-methyl (520.4mol) is introduced in 1m
3In 185 liters of methyl alcohol in the steel container.Adding 19.0g is dissolved in (RophosARhCOD) CF in 2 liters of methyl alcohol
3SO
3(=26mmol preformed catalyst, s/c 20,000/1) then clung under the hydrogen at 50 ℃, 4 and carried out hydrogenation.The conversion of substrate was finished after 4 hours.The enantiomeric excess of this hydrogenated products is determined as the 99.4% (manufacturers of post: Chiracel by chirality HPLC; Column type: OD-H; Moving phase: 95vol% normal heptane/5vol%2-propyl alcohol-this mixture of 0.1ml trifluoroacetic acid/1L; Retention time:
t
R((R)-2-methylsuccinic acid 4-methyl ester)=7.4 minutes
t
R((S)-2-methylsuccinic acid 4-methyl ester)=16.7 minutes).
In reaction soln, gradation adds total 22.2kg lithium hydroxide monohydrate, then adds the 375kg methyl tertiary butyl ether, is cooled to 0 ℃.By filtering the carboxylic acid lithium is removed (yield: 65.8kg) from the suspension that obtains.Its enantiomeric excess (after release, measuring)>99.8%.
Embodiment 5
On-site preparation preformed catalyst (general step)
With 1.1 normal RophosA-Bistriflate salt (Rophos*2CF
3SO
3H) be dissolved in methyl alcohol with 1.1 equivalent alkali (preferred amines such as triethylamine, H ü nig ' s alkali etc.), and under-10 ℃, slowly splash into 1 normal source metal, preferred (Rh[COD]
2) in the solution of X, X=BF wherein
4, CF
3SO
3, SbF
6, PF
6, ClO
4, BAr
4Make this mixture reach room temperature then.If the use free ligand does not then add alkali.
Claims (17)
1. the method for a preparation formula (I) optically active alkyl succinic acid monoalkyl esters,
Wherein D and E are H, C independently of one another
1-C
10Alkyl,
R is C
1-C
10Alkyl, phenyl or benzyl,
This method in the presence of the catalyzer that comprises formula (L) phospholane part,
Wherein:
R
1Be hydrogen, C
1-C
6Alkyl or benzyl,
R
2Be C
1-C
6Alkyl or benzyl,
A is R
1Or
Condition be B=between two P atoms, have 1-5 carbon atom the connection base or
Cp-Fe-Cp,
Enantioselectivity ground hydrogenation of formula (II) compound
Wherein D, E and R have above-mentioned meaning.
2. the method for claim 1, wherein D and E are that hydrogen and R are Me.
4. the method for claim 1, wherein said hydrogenation is carried out under the hydrogen pressure of 1-100 crust.
5. the method for claim 1, wherein said hydrogenation is carried out in methyl alcohol.
6. the method for claim 1, wherein said hydrogenation is carried out under 10 ℃-80 ℃.
7. the method for claim 1, use therein catalyzer is fixed.
8. the method for claim 1, wherein the reaction product that is obtained by hydrogenation (I) is converted into carboxylate salt and removes from this reaction mixture with this form.
9. method as claimed in claim 8, wherein said reaction product (I) precipitates from this reaction mixture with the form of carboxylic acid lithium.
10. the method for a preparation formula (I) optically active alkyl succinic acid monoalkyl esters,
Wherein D and E are H, C independently of one another
1-C
10Alkyl,
R is C
1-C
10Alkyl, phenyl or benzyl,
This method in the presence of comprising the catalyzer that is selected from the part among Me-KetalPhos and the Me-f-KetalPhos,
Enantioselectivity ground hydrogenation of formula (II) compound
Wherein D, E and R have above-mentioned meaning.
11. method as claimed in claim 10, wherein D and E are that hydrogen and R are Me.
12. method as claimed in claim 10, wherein said hydrogenation is carried out under the hydrogen pressure of 1-100 crust.
13. method as claimed in claim 10, wherein said hydrogenation is carried out in methyl alcohol.
14. method as claimed in claim 10, wherein said hydrogenation is carried out under 10 ℃-80 ℃.
15. method as claimed in claim 10, use therein catalyzer is fixed.
16. method as claimed in claim 10, wherein the reaction product that is obtained by hydrogenation (I) is converted into carboxylate salt and removes from this reaction mixture with this form.
17. method as claimed in claim 16, wherein said reaction product (I) precipitates from this reaction mixture with the form of carboxylic acid lithium.
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DE200410032968 DE102004032968A1 (en) | 2004-07-07 | 2004-07-07 | Preparation of optically active alkyl succinic acid monoalkyl esters comprising enantioselective hydrogenation of ester compound in presence of catalyst, which carries phospholane ligand |
DE102004032968.0 | 2004-07-07 | ||
DE102005007750.1 | 2005-02-18 | ||
DE200510007750 DE102005007750A1 (en) | 2005-02-18 | 2005-02-18 | Preparation of optically active alkyl succinic acid monoalkyl esters comprising enantioselective hydrogenation of ester compound in presence of catalyst, which carries phospholane ligand |
PCT/EP2005/007289 WO2006002999A2 (en) | 2004-07-07 | 2005-07-06 | Method for the production of optically active alkyl succinic acid monoalkyl esters |
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US6043396A (en) * | 1997-06-18 | 2000-03-28 | Basf Aktiengesellschaft | Preparation of optically active phospholanes, their metal complexes and use in asymmetric synthesis |
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2004
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US6043396A (en) * | 1997-06-18 | 2000-03-28 | Basf Aktiengesellschaft | Preparation of optically active phospholanes, their metal complexes and use in asymmetric synthesis |
Non-Patent Citations (4)
Title |
---|
Duncan carmichael, et al.Hybrid P-chiral diphosphines for asymmetric hydrogenation.Chem. Commun. 3.1999,(3),261-262. |
Duncan carmichael,et al.Hybrid P-chiral diphosphines for asymmetric hydrogenation.Chem.Commun. 3.1999,(3),261-262. * |
Jens Holz, et al.Synthesis of a new class of functionalized chiralbisphospholane ligands and the application inenantioselective hydrogenations.J. org. chem63 22.1998,63(22),8031-8034. |
Jens Holz,et al.Synthesis of a new class of functionalized chiralbisphospholane ligands and the application inenantioselective hydrogenations.J.org. chem63 22.1998,63(22),8031-8034. * |
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