TWI443083B - 氫甲化醯化方法 - Google Patents
氫甲化醯化方法 Download PDFInfo
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- TWI443083B TWI443083B TW096128971A TW96128971A TWI443083B TW I443083 B TWI443083 B TW I443083B TW 096128971 A TW096128971 A TW 096128971A TW 96128971 A TW96128971 A TW 96128971A TW I443083 B TWI443083 B TW I443083B
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- Prior art keywords
- bis
- catalyst
- cyclobutane
- trans
- ruthenium complex
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- 238000000034 method Methods 0.000 title claims description 27
- 238000007037 hydroformylation reaction Methods 0.000 title description 14
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims description 32
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 25
- PIAOXUVIBAKVSP-UHFFFAOYSA-N γ-hydroxybutyraldehyde Chemical compound OCCCC=O PIAOXUVIBAKVSP-UHFFFAOYSA-N 0.000 claims description 24
- 239000012327 Ruthenium complex Substances 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 239000003446 ligand Substances 0.000 claims description 16
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 claims description 14
- -1 monophosphine compound Chemical class 0.000 claims description 11
- 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 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- REZOVLQIMMUCQH-HEVIKAOCSA-N [(1r,2r)-2-[bis(3,5-dimethylphenyl)phosphanylmethyl]cyclobutyl]methyl-bis(3,5-dimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC(P(C[C@H]2[C@@H](CC2)CP(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)=C1 REZOVLQIMMUCQH-HEVIKAOCSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 3
- 150000004678 hydrides Chemical class 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- LDEYMTKDLFRIBZ-COCZKOEFSA-N [(1r,2r)-2-[bis(3,5-diethylphenyl)phosphanylmethyl]cyclobutyl]methyl-bis(3,5-diethylphenyl)phosphane Chemical compound CCC1=CC(CC)=CC(P(C[C@H]2[C@@H](CC2)CP(C=2C=C(CC)C=C(CC)C=2)C=2C=C(CC)C=C(CC)C=2)C=2C=C(CC)C=C(CC)C=2)=C1 LDEYMTKDLFRIBZ-COCZKOEFSA-N 0.000 claims 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- JTMCAHGCWBGWRV-UHFFFAOYSA-N 3-hydroxy-2-methylpropanal Chemical compound OCC(C)C=O JTMCAHGCWBGWRV-UHFFFAOYSA-N 0.000 description 15
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- 239000001273 butane Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003303 ruthenium Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- NBIQQWVRJJWYQC-YUMQZZPRSA-N 2-[(1S,2S)-2-(2-hydroxyethyl)cyclobutyl]ethanol Chemical compound OCC[C@H]1[C@@H](CC1)CCO NBIQQWVRJJWYQC-YUMQZZPRSA-N 0.000 description 1
- KMADTHJCHZCGJZ-UHFFFAOYSA-N 4-hydroxybutanal;3-hydroxy-2-methylpropanal Chemical compound OCC(C)C=O.OCCCC=O KMADTHJCHZCGJZ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- KMTTUERWIBEAEN-UIOOFZCWSA-N [(1r,2r)-2-(diphenylphosphanylmethyl)cyclobutyl]methyl-diphenylphosphane Chemical compound C([C@@H]1CC[C@H]1CP(C=1C=CC=CC=1)C=1C=CC=CC=1)P(C=1C=CC=CC=1)C1=CC=CC=C1 KMTTUERWIBEAEN-UIOOFZCWSA-N 0.000 description 1
- JNSOWRGURGFGDS-KYJUHHDHSA-N [(1r,2r)-2-[bis(4-methylphenyl)phosphanylmethyl]cyclobutyl]methyl-bis(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C[C@H]1[C@H](CP(C=2C=CC(C)=CC=2)C=2C=CC(C)=CC=2)CC1 JNSOWRGURGFGDS-KYJUHHDHSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- GPFIUEZTNRNFGD-UHFFFAOYSA-N bis(3,5-dimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC(PC=2C=C(C)C=C(C)C=2)=C1 GPFIUEZTNRNFGD-UHFFFAOYSA-N 0.000 description 1
- RRSCGNXXNRAXJC-UHFFFAOYSA-N bis(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1PC1=CC=C(C)C=C1 RRSCGNXXNRAXJC-UHFFFAOYSA-N 0.000 description 1
- PMCLRBQCDGAJJW-UHFFFAOYSA-N bis(oxomethylidene)ruthenium Chemical compound O=C=[Ru]=C=O PMCLRBQCDGAJJW-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 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
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- PXCVPYJXMUOIMP-UHFFFAOYSA-N formaldehyde;ruthenium;triphenylphosphane Chemical compound [Ru].O=C.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 PXCVPYJXMUOIMP-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 229940100573 methylpropanediol Drugs 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 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
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000012487 rinsing solution Substances 0.000 description 1
- SNOOUWRIMMFWNE-UHFFFAOYSA-M sodium;6-[(3,4,5-trimethoxybenzoyl)amino]hexanoate Chemical compound [Na+].COC1=CC(C(=O)NCCCCCC([O-])=O)=CC(OC)=C1OC SNOOUWRIMMFWNE-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
-
- 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
-
- 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
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
- C07C47/19—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5027—Polyphosphines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
-
- 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
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0258—Flexible ligands, e.g. mainly sp3-carbon framework as exemplified by the "tedicyp" ligand, i.e. cis-cis-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane
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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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
本發明係關於一種氫甲醯化烯丙醇以產生4-羥基丁醛之方法。本方法產生出乎預期的高比例之4-羥基丁醛:3-羥基-2-甲基丙醛的產物(線性:分支)。
烯丙醇的氫甲醯化是已知的且為商業上施行之方法。參見例如USP 4064145,4215077,4238419,4678857及5290743。在氫甲醯化反應中,烯丙醇是在觸媒存在下與CO/H2
氣體混合物反應,以形成4-羥基丁醛(HBA)。HBA可然後例如藉由水的萃取從觸媒中分離,再氫化形成1-丁二醇(BDO)。參見USP 5504261。
已經利用各種不同之系統於氫甲醯化反應中,最特別是銠複合物和膦配位體(參見例如USP 4064145,4238419及4567305)。常見使用的膦配位體為經三取代的膦類,例如三苯基膦。氫甲醯化方法之一個缺點為除了所欲的HBA線性產物外,也形成了其它連產物或副產物。烯丙醇的氫甲醯化典型產生了一些3-羥基-2-甲基丙醛(HMPA)分支連產物及C3
副產物,例如正-丙醇和丙醛。儘管HMPA可被氫化產生有用的物質,1,3-甲基丙二醇(MPD),但是MPD連產物降低了BDO之產率。C3
副產物之形成代表方法中另外的產率損失,其可對製程經濟方面具有嚴重不利的影響。
為了增加BDO產率,持續地研究以改良氫甲醯化方法和降低較少的所欲連產物/副產物。USP 6127584揭示使用具有至少兩個甲基之三烷基膦配位體可導致增加的HBA:HMPA比例。已經發現使用二膦配位體可改良HBA:HMPA比例。在技藝,特別是日本公開申請案06-279345及06-279344以及USP4306087中已顯示了使用銠複合物觸媒及二膦配位體(例如DIOP或反式-1,2-雙(二苯基-膦甲基)環丁烷的烯丙醇之氫甲醯化反應。USP 6225509揭示當使用由銠複合物和例如DIOP之配位體所組成之觸媒時,維持反應液體中CO濃度在高於約4.5毫莫耳/升可降低不欲的C3
連產物之產生。此外,同申請中的US專利申請序號11/580510揭示使用2,3-O-異亞丙基-2,3-二羥基-1,4-雙[雙(3,5-二-正-烷基苯基)膦]丁烷配位體產生了與3-羥基-2-甲基丙醛相較下高產率的4-羥基丁醛。
總之,需要一種用於氫甲醯化烯丙醇以產生4-羥基丁醛之新穎方法。尤其有用的方法產生了與3-羥基-2-甲基丙醛(HMPA)相較下高產率的4-羥基丁醛(HBA)。
本發明是一種包括在溶劑和觸媒系統存在下使烯丙醇和一氧化碳與氫氣反應以產生4-羥基丁醛的方法。該觸媒系統包括銠複合物和反式-1,2-雙(雙(3,5-二-正-烷基苯基)膦甲基)環丁烷。本發明令人驚訝地產生與3-羥基-2-甲基丙醛相較下高比例的4-羥基丁醛產物。
本發明之方法包括在溶劑和觸媒系統存在下氫甲醯化烯丙醇。本發明之觸媒系統包括銠複合物和反式-1,2-雙(雙(3,5-二-正-烷基苯基)膦甲基)環丁烷。反式-1,2-雙(雙(3,5-二-正-烷基苯基)膦甲基)環丁烷具有下列化學式:
其中R為正-烷基。較佳地,R為甲基,乙基或丙基。
二膦配位體最佳地為反式-1,2-雙(雙(3,5-二甲基苯基)膦甲基)環丁烷或是反式-1,2-雙(雙(3,5-二乙基苯基)膦甲基)環丁烷。
可以藉由任何可能的方法製備反式-1,2-雙(雙(3,5-二-正-烷基苯基)膦甲基)環丁烷。例如,可藉由反式-1,2-環丁烷二甲醇,雙(甲苯磺酸鹽)與二(3,5-二-正-烷基苯基)膦酸鋰反應來製備之。
本發明之觸媒系統包括銠複合物。合適的銠複合物包含連接到配位基上的銠。銠複合物較佳可溶於溶劑中。對於與銠複合物連接之配位體的選擇並沒有特別的限制。例如,合適的配位體包括氫化物,羰基,經取代及未經取代的環戊二烯基,2,4-烷二酸酯,三烷基或三芳基膦,二膦類及其混合物。特別較佳的配位體包括羰基,乙醯基丙酮(2,4-戊二酸酯),三苯基膦及其混合物。較佳的銠複合物之實例包括(乙醯基丙酮根)二羰基銠及三(三苯基膦)銠羰基氫化物。
銠複合物可在使用於氫甲醯化前先與反式-1,2-雙(雙(3,5-二-正-烷基苯基)膦甲基)環丁烷預先結合,使得雙(雙(3,5-二-正-烷基苯基)膦甲基)環丁烷配位體形成部分的銠複合物,或是其可個別地添加。然而,較佳為與反式-1,2-雙(雙(3,5-二-正-烷基苯基)膦甲基)環丁烷分開加入銠複合物。反式-1,2-雙(雙(3,5-二-正-烷基苯基)膦甲基)環丁烷:銠複合物之莫耳比例較佳是在0.5:1到5:1的範圍內。
僅管不是必要的,觸媒系統可額外包括單膦化合物。單膦化合物為除了可與銠複合物產生結合之任何膦配位體。單膦化合物為經三取代的膦,其可由下式表示:(R1
)3
P其中R1
為芳基或烷基。合適的脂肪族R1
基包括甲基,乙基,正-丁基,第二-丁基,辛基及癸基。合適的芳族R1
基包括苯基,甲苯基及萘基。R1
基可為相同或不同的,但較佳為相同的。較佳地,單膦為經三取代芳基膦。更佳地,單膦為三苯基膦或三甲苯基膦。三苯基膦為特別較佳的。
本發明之方法亦需要反應溶劑。典型溶劑為能溶解銠複合物且不會與在氫甲醯化步驟中產生的羥基醛類反應之溶劑。合適的溶劑包括任何在水中具有非常低或最小溶解度之有機溶劑。較佳溶劑包括C5
-C20
脂肪族碳氫化合物,C6
-C20
芳香族碳氫化合物,醇類,醚類及其混合物。特別較佳的溶劑包括甲苯,環己烷,甲基第三-丁基醚及其混合物。
用於氫甲醯化步驟之典型反應條件是對於形成線性4-羥基丁醛(HBA)而非分支的3-羥基-2-甲基丙醛(HMPA)反應產物而言是溫和到有利的。反應條件較佳是在從約20到120℃的範圍內,且壓力是在從約20到600psig的範圍內,更佳是在從約45到85℃以及30到400psig的範圍內,且最佳是在約50到80℃以及40到300psig的範圍內。CO:H2
的莫耳比例典型是在約1:1,儘管該比例可相當大的變化。CO的分壓典型是在5到100psig的範圍內。氫氣的分壓典型是在40到200psig的範圍內。反應是在這些條件下進行,直到多數烯丙醇的已經反應了,例如60到99.9%,產物主要為具有少許分支的反應產物之4-羥基丁醛。反應時間的數量不是關鍵的,但通常0.5到4小時的反應時間是合適的。
以反應溶劑對進料為基礎,烯丙醇起始濃度在溶劑中為約5到40重量%的範圍,更佳地,可使用在5到10重量%範圍內的較低濃度。
較佳地,進行烯丙醇之氫甲醯化,使得在液相([CO]liq
)中的CO濃度於氫甲醯化期間維持在高於4毫莫耳/升(0.004M)。[CO]liq
的數值是定義在USP 6225509中,其之教示併入本文中為參考用。較佳地,液相氫:一氧化碳之莫耳比例是在10:1到約1:2的範圍內,更佳是在5:1到約1:2的範圍內。
在氫甲醯化步驟後,HBA產物較佳在萃取容器中藉由水的萃取從溶劑及觸媒系統中分離。水的萃取方法在技藝中是已經習知的且可藉由任何合適的裝置,例如混合器-沉降器,填充或盤式萃取塔,旋轉盤接觸器來進行或送經沉降槽中,以使混合物離析成水相和有機相。HBA及任何HMPA在水(含水)相中維持著可溶解且可從溶劑(有機)相中分離出。
4-羥基丁醛(及任何3-羥基-2-甲基丙醛)反應產物較佳在氫化觸媒存在下接受額外的氫化4-羥基丁醛之步驟以產生1,4-丁二醇(BDO)。氫氣被加入到反應容器中以氫化用。合適的氫化觸媒包括任何第VIII族金屬,例如鎳,鈷,鉑及鈀,以及銅,鋅和鉻,及其混合物和合金。特別較佳為鎳觸媒。最佳為Raney型鎳及固定床鎳觸媒。
氫化反應條件較佳是在從約60到200℃以及壓力為約200到1000psig的範圍內,更佳是在約80到140℃以及300到1000psig的範圍內。一般而言,合適的反應時間是1到10小時。在氫化反應期間,雖然實質上保留了高比例的線性對分支產物,BDO和MPD會隨同其它低的連產物/副產物生成。
下述實施例僅為說明本發明。熟習該項技術者將瞭解許多在本發明精神和申請專利範圍之範疇內的變化。
1A,1B和1C:下列通式之二膦1A,1B和1C係如下述製備。
在氬氣下,逐滴滴入一種反式-1,2-環丁二甲醇,雙(甲苯磺酸鹽)溶於乾燥/經除氣THF(1當量,1.73克,3.7×10-3
莫耳的二噁烷溶於50毫升THF中)中之溶液到一種適當的二芳基膦酸鋰(參見上式)溶於乾燥/經除氣THF(2.3當量溶於100毫升THF中)中之溶液。混合物於回流下加熱2小時,然後冷卻,再於減壓下除去溶劑。剩餘的固體再溶於二氯甲烷中,經由矽石床過濾,再於減壓下除去溶劑以產生反式-1,2-雙(二芳基膦甲基)環丁烷。
二膦1A:反式-1,2-雙(雙(3,5-二甲基苯基)膦甲基)環丁烷。
比較性二膦1B:反式-1,2-雙(雙(4-甲基苯基)膦甲基)環丁烷。
比較性二膦1C:反式-1,2-雙(二苯基膦甲基)環丁烷。
1D,1E和1F:下列通式之二膦1D,1E和1F係如下述製備。
在氬氣下,逐滴滴入一種2,2-二甲基-4,5-雙[(甲苯磺醯基氧基甲基)甲基]-1,3-二噁烷溶於乾燥/經除氣THF(1當量,1.73克,3.7×10-3
莫耳的二噁烷溶於50毫升THF中)中之溶液到一種適當的二芳基膦鋰鹽(參見上式)溶於乾燥/經除氣THF(2.3當量溶於100毫升THF中)中之溶液。混合物於回流下加熱2小時,然後冷卻,再於減壓下除去溶劑。剩餘的固體再溶於二氯甲烷中,經由矽石床過濾,再於減壓下除去溶劑以產生2,3-O-異亞丙基-2,3-二羥基-1,4-雙(二芳基)膦丁烷。
比較性二膦1D:2,3-O-異亞丙基-2,3-二羥基-1,4-雙[雙(3,5-二甲基苯基)膦]丁烷。
比較性二膦1E:2,3-O-異亞丙基-2,3-二羥基-1,4-雙[雙(4-甲基苯基)膦]丁烷。
比較性二膦1F:2,3-O-異亞丙基-2,3-二羥基-1,4-雙[雙苯基)膦]丁烷,習知為DIOP。
根據下列程序來使用二膦1A-1F來氫甲醯化烯丙醇。
於100毫升的Parr自熱釜中,使一種所欲之二膦溶液(2當量或8.6×10-5
莫耳)溶於乾燥經除氣甲苯(15克)中之溶液加入[Rh(CO)2
(acac)](1當量或4.3×10-5
莫耳)中。使用1:1CO/H2
混合物沖洗溶液三次,然後再使用CO/H2
混合物加壓到180psig。然後使用攪拌,加熱自熱釜到65℃,注射烯丙醇(3.5毫升),再使用CO/H2
混合物加壓到200psig。自熱釜維持在200psig的固定壓力下,再監測反應的氣體吸收。當沒有進一步的氣體吸收時,冷卻自熱釜,再減壓。使用氣相層析分析所得溶液以決定反應的產物。反應產生HBA、HMPA及C3
產物(正-丙醇和丙醛)。
如表1所示之結果證明了本發明之反式-1,2-雙(雙(3,5-二-正烷基苯基)膦甲基)環丁烷出乎預期地產生了相較於任何其它比較性二膦而言明顯較高的HBA:HMPA(1:b)。
Claims (15)
- 一種產生4-羥基丁醛之方法,其包括在溶劑和觸媒系統存在下使烯丙醇和一氧化碳與氫氣反應,該觸媒系統包括銠複合物和反式-1,2-雙(雙(3,5-二-正-烷基苯基)膦甲基)環丁烷。
- 如申請專利範圍第1項之方法,其中觸媒系統包括銠複合物和反式-1,2-雙(雙(3,5-二-甲基苯基)膦甲基)環丁烷。
- 如申請專利範圍第1項之方法,其中觸媒系統包括銠複合物和反式-1,2-雙(雙(3,5-二-乙基苯基)膦甲基)環丁烷。
- 如申請專利範圍第1項之方法,其中溶劑為選自由C5 -C20 脂肪族碳氫化合物,C6 -C12 芳香族碳氫化合物,醚類,醇類,及其混合物所組成之族群中。
- 如申請專利範圍第1項之方法,其中溶劑為選自由甲苯,環己烷,甲基第三-丁基醚及其混合物所組成之族群中。
- 如申請專利範圍第1項之方法,其中銠複合物包括銠及選自由氫化物,羰基,三烷基或三芳基膦,二膦類,環戊二烯基,2,4-烷二酸酯,及其混合物所組成之族群中的配位體。
- 如申請專利範圍第1項之方法,其中反應是在從約45到約85℃之範圍的溫度以及約30到約400psig之範圍的壓力下進行的。
- 如申請專利範圍第1項之方法,其中該觸媒系統進一 步包括單膦化合物。
- 如申請專利範圍第8項之方法,其中該單膦化合物為三苯基膦。
- 如申請專利範圍第1項之方法,其進一步包括在氫化觸媒存在下氫化4-羥基丁醛以形成1,4-丁二醇。
- 如申請專利範圍第10項之方法,其中氫化觸媒為鎳觸媒。
- 一種觸媒,其包括銠複合物和反式-1,2-雙(雙(3,5-二-正-烷基苯基)膦甲基)環丁烷。
- 如申請專利範圍第12項之觸媒,其中該觸媒系統包括銠複合物和反式-1,2-雙(雙(3,5-二-甲基苯基)膦甲基)環丁烷。
- 如申請專利範圍第12項之觸媒,其中該觸媒系統包括銠複合物和反式-1,2-雙(雙(3,5-二-乙基苯基)膦甲基)環丁烷。
- 如申請專利範圍第12項之觸媒,其中該銠複合物包括銠和選自由氫化物,羰基,三烷基或三芳基膦,二膦,環戊二烯基,2,4-烷二酸酯,及其混合物所組成之族群中的配位體。
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US7279606B1 (en) | 2007-10-09 |
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