TWI408121B - 氫甲醯化方法 - Google Patents
氫甲醯化方法 Download PDFInfo
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- TWI408121B TWI408121B TW096104363A TW96104363A TWI408121B TW I408121 B TWI408121 B TW I408121B TW 096104363 A TW096104363 A TW 096104363A TW 96104363 A TW96104363 A TW 96104363A TW I408121 B TWI408121 B TW I408121B
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- Prior art keywords
- bis
- phosphine
- group
- isopropylidene
- dihydroxy
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000007037 hydroformylation reaction Methods 0.000 title description 18
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims abstract description 30
- PIAOXUVIBAKVSP-UHFFFAOYSA-N γ-hydroxybutyraldehyde Chemical compound OCCCC=O PIAOXUVIBAKVSP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000001273 butane Substances 0.000 claims abstract description 23
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 23
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 45
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims description 42
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 23
- 239000003446 ligand Substances 0.000 claims description 20
- 239000012327 Ruthenium complex Substances 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 12
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 7
- -1 monophosphine compound Chemical class 0.000 claims description 7
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-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
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000004678 hydrides Chemical class 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229910002090 carbon oxide Inorganic materials 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- JTMCAHGCWBGWRV-UHFFFAOYSA-N 3-hydroxy-2-methylpropanal Chemical compound OCC(C)C=O JTMCAHGCWBGWRV-UHFFFAOYSA-N 0.000 abstract description 16
- 239000010948 rhodium Substances 0.000 abstract description 4
- 229910052703 rhodium Inorganic materials 0.000 abstract description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 abstract description 3
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-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
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 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 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 230000035484 reaction time Effects 0.000 description 2
- 150000003283 rhodium Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- 239000007983 Tris buffer Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 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
- 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- NBXSLXZWWHEDPI-UHFFFAOYSA-N bis(2,4,6-trimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC(C)=C1PC1=C(C)C=C(C)C=C1C NBXSLXZWWHEDPI-UHFFFAOYSA-N 0.000 description 1
- JOVHNTIMXPAYOU-UHFFFAOYSA-N bis(4-chlorophenyl)phosphane Chemical compound C1=CC(Cl)=CC=C1PC1=CC=C(Cl)C=C1 JOVHNTIMXPAYOU-UHFFFAOYSA-N 0.000 description 1
- VNKFDSUAELUAQZ-UHFFFAOYSA-N bis(4-methoxy-3,5-dimethylphenyl)phosphane Chemical compound C1=C(C)C(OC)=C(C)C=C1PC1=CC(C)=C(OC)C(C)=C1 VNKFDSUAELUAQZ-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
- OTQIBIWGQUJMOM-UHFFFAOYSA-N bis[3,5-bis(trifluoromethyl)phenyl]phosphane Chemical compound FC(F)(F)C1=CC(C(F)(F)F)=CC(PC=2C=C(C=C(C=2)C(F)(F)F)C(F)(F)F)=C1 OTQIBIWGQUJMOM-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
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 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
- 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
- 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
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012716 precipitator Substances 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
- 238000010992 reflux Methods 0.000 description 1
- 239000000377 silicon dioxide 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
- 239000007787 solid Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
-
- 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
-
- 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
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本發明關於一種使烯丙醇氫甲醯化而產生4-羥丁醛的方法。該方法產生非預期的高4-羥丁醛:3-羥基-2-甲基丙醛(線性:分支)產物之比例。
烯丙醇之氫甲醯化為一種習知的且在商業上實行的方法。舉例而言,可參見USP 4,064,145、4,215,077、4,238,419、4,678,857、和5,290,743。在氫甲醯化反應中,烯丙醇係在存有觸媒之情況下與CO/H2
氣體混合物反應而形成4-羥丁醛(HBA)。然後,HBA可能例如藉由水的萃取而從觸媒中分離,並氫化而形成1,4-丁二醇(BDO)。參見USP 5,504,261。
已有許多不同之觸媒系統被用於氫甲醯化反應中,最值得注意的為一種銠錯合物連同一種膦配位基(參見,例如:USP 4,064,145、4,238,419和4,567,305)。一般所使用的膦配位基為三取代基膦,例如三苯基膦。氫甲醯化反應的一種缺點為,除了所欲的HBA線性產物外,亦會形成其他共產物或副產物。烯丙醇之氫甲醯化典型而言會產生一些3-羥基-2-甲基丙醛(HMPA)之分支性共產物,以及C3
副產物,例如正丙醇和丙醛。雖然可使HMPA氫化而產生有用的物質1,3-甲基-丙二醇(MPD),但MPD副產物會降低BDO的產率。C3
副產物的形成實際上代表著在該方法中
另一種產率的損失,其可能對於該方法之經濟效益而言產生嚴重的反效果。
為了增加BDO的產率,研究上持續地進行氫甲醯化方法的改善,並減少較不需要的共產物/副產物。USP 6,127,584揭示具有至少2個甲基之三烷基膦配位基之用途,其結果會使HBA:HMPA之比例增加。二膦配位基的使用亦被發現可增加HBA:HMPA之比例。使用銠錯合物觸媒和DIOP二膦配位基以進行烯丙醇之氫甲醯化可見於先前技術中,尤其是日本公開公報編號06-279345和06-279344,以及USP 4,306,087。此外,USP 6,225,509揭示在使用一種包含有一種銠錯合物和一種例如DIOP之配位基的烯丙醇氫甲醯化反應中,將反應液相中之CO濃度維持高於約4.5 mmols/L時可減少不需要之C3
共產物的生成。
簡言之,有需要新的方法以使烯丙醇氫甲醯化而產生4-羥丁醛。特別有用的方法將可產生相較於3-羥基-2-甲基丙醛(HMPA)而言高的4-羥丁醛(HBA)的比例。
本發明為一種包含使烯丙醇與一氧化碳和氫氣在存有一種溶劑和觸媒系統之情況下反應而產生4-羥丁醛的方法。該觸媒系統包括銠錯合物和2,3-O
-亞異丙基-2,3-二羥基-1,4-雙[雙(3,5-二-正-烷基苯基)膦]丁烷。本發明令人驚訝地導致相較於3-羥基-2-甲基丙醛而言高的4-羥丁醛的比例。
本發明之方法包括在存有一溶劑和一觸媒系統下使烯丙醇氫甲醯化。本發明之觸媒系統包括銠錯合物以及2,3-O
-亞異丙基-2,3-二羥基-1,4-雙[雙(3,5-二-正-烷基苯基)膦]丁烷。合適的銠錯合物包含與配位基基團連接之銠。銠錯合物可溶於溶劑中。關於與銠錯合物連接之配位基的選擇並無特定的限制。舉例而言,合適的配位基包括氫化物、羰基、經取代和未經取代之環戊二烯基、2,4-烷二酸鹽(2,4-alkanedionate)、三烷基或三芳香膦、二膦以及其混合物。特別較佳的配位基包括羰基、乙醯丙酮酸鹽(acetylacetonate)(2,4-戊二酸鹽(pentanedionate))、三苯基膦以及其混合物。較佳的銠錯合物之實例包括(乙醯基丙酮根(acetylacctonato))二羰基銠和三(三苯基膦)氫化羰基銠。
本發明之觸媒系統亦包括二膦配位基,2,3-O
-亞異丙基-2,3-二羥基-1,4-雙[雙(3,5-二-正-烷基苯基)膦]丁烷。2,3-O
-亞異丙基-2,3-二羥基-1,4-雙[雙(3,5-二-正-烷基苯基)膦]丁烷具有化學通式:
其中R為正烷基。較佳地,R為甲基、乙基或丙基。
最佳的二膦配位基為2,3-O
-亞異丙基-2,3-二羥基-1,4-雙[雙(3,5-二甲基苯基)膦]丁烷或2,3-O
-亞異丙基-2,3-二羥基-1,4-雙[雙(3,5-二乙基苯基)膦]丁烷。
2,3-O
-亞異丙基-2,3-二羥基-1,4-雙[雙(3,5-二-正-烷基苯基)膦]丁烷可由任何可能的方法製得。舉例而言,其可由2,2-二甲基-4,5-雙[(甲苯磺醯氧基甲基)甲基]-1,3-二氧戊烷與二(3,5-二-正烷基苯基)膦鋰反應而製得。
2,3-O
-亞異丙基-2,3-二羥基-1,4-雙[雙(3,5-二-正-烷基苯基)膦]丁烷配位基可在使用於氫甲醯化反應前預先與銠錯合物結合,或可個別地添加。然而,較佳的為使2,3-O
-亞異丙基-2,3-二羥基-1,4-雙[雙(3,5-二-正-烷基苯基)膦]丁烷配位基與銠錯合物分別添加。
雖不需要,觸媒系統可額外地包括一單膦化合物。單膦化合物為除任何膦配位基外可與銠錯合物結合者。單膦化合物為經三取代的膦,其係以下述通式表示:
(R1
)3
P
其中R1
係芳基或烷基。合適的脂肪族R1
基團包括甲基、乙基、正丁基、第二丁基、辛基和癸基。合適的芳香族R1
基團包括苯基、甲苯基和萘基。R1
基團可為相同或不同,但較佳為相同。較佳地,單膦為經三取代的芳基膦。更佳地,單膦為三苯基膦或三甲苯基膦。特別較佳的為三苯基膦。
反應溶劑亦為本發明之方法所需。典型的溶劑為能將銠錯合物溶解且不會與由氫甲醯化步驟中產生之羥基醛反應者。合適的溶劑包括具有極低或最小水中溶解度之任何有機溶劑。較佳的溶劑包括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。
典型的氫甲醯化步驟之反應條件為溫和的,以利於線性4-羥丁醛(HBA)而不是分支3-羥基-2-甲基丙醛(HMPA)反應產物的形成。反應條件較佳係自約20至120℃之範圍內,而壓力則自約20至600 psig,更佳為自約45至85℃與30至400 psig,最佳為自約50至80℃與40至400 psig。CO:H2
之莫耳數比典型而言為約1:1,雖然比例可相當程度的改變。CO之分壓典型而言在5至100 psig之範圍內。氫氣之分壓典型而言在40至200 psig之範圍內。反應則在這些條件下執行,直到大部分之烯丙醇被反應,例如60至99.9%,而產物則大部分為4-羥丁醛以及一些分支的反應產物。通常1至4小時之反應時間為適當的。
較佳地,烯丙醇之起始濃度,根據進料反應溶劑之基準而言,在反應溶劑中約佔5至40重量%;更佳地,可使用範圍為5至10重量%之較低濃度。
較佳地,烯丙醇之氫甲醯化係在氫甲醯化期間使CO在液相中之濃度([CO]liq
)維持在高於4 mmols/升(0.004 M)之情況下執行。[CO]liq
之值係定義在USP 6,225,509中,而其教示則以引用方式納入本文中。較佳地,液相中之氫氣:一氧化碳之莫耳數比在自10:1至約1:2之範圍內,更佳的為自5:1至約1:2。
在氫甲醯化步驟之後,較佳為藉由在一萃取槽中以水萃取方式將HBA產物自溶劑與觸媒系統中分離。水萃取法為先前技術所習知,且可以任何合適的裝置進行,例如混合器-沈澱器、填充或盤式萃取管柱、轉盤式接觸器,或使其通過沈澱槽以將混合物溶解至水相或有機相中。HBA以及任何HMPA仍溶解在水相(水溶液)中,且自溶劑相(有機)中分離。
4-羥丁醛(以及任何之3-羥基-2-甲基丙醛)之反應產物較佳被施以額外的步驟,以在存有氫化觸媒下,將4-羥丁醛氫化以製造1,4-丁二醇(BDO)。將氫氣添加至反應槽中以進行氫化反應。合適的氫化觸媒包括任何第八族金屬,例如鎳、鈷、釕、鉑、和鈀,以及銅、鋅和鉻及其混合物和合金。特別較佳的為鎳觸媒。最佳的為Raney型鎳和固定床鎳觸媒。
氫化反應條件較佳是在自約60至200℃以及自約200至1000 psig之壓力範圍內,更佳的為自約80至140℃以及300至1000 psig。一般而言,適當之反應時間為1至10小時。在氫化反應中形成BDO和MPD,同時在實質上保有線型與分支產物之比例,以及其他低量的共-產物/副產物。
下述實例僅說明本發明。熟習本項技術者要瞭解許多變體皆需在本發明之精神和申請專利範圍之範疇內。
具有以下化學通式之二膦配位基係如下述而製備。
在氬氣存在下,將一種溶於乾燥/除氣之THF中之2,2-二甲基-4,5-雙[(甲苯磺醯氧基甲基)甲基]-1,3-二氧戊烷溶液(1當量,1.73 g,3.7×10-3
莫耳二氧戊烷溶於50 mL THF中)逐滴加入適當之溶於乾燥/除氣之THF中之二芳基膦鋰(參見以上化學式)之溶液(2.3當量溶於100 mL THF中)中。混合物係回流加熱2小時,然後冷卻,在減壓情況下將溶劑移除。將剩餘的固體再溶解於二氯甲烷中,經由矽石床過濾,並在減壓情況下將溶劑移除而產生2,3-O
-亞異丙基-2,3-二羥基-1,4-雙(二芳香羥基膦)丁烷。
二膦1A
:2,3-O
-亞異丙基-2,3-二羥基-1,4-雙[雙(3,5-二甲基苯基)膦]丁烷。
二膦1B
:2,3-O
-亞異丙基-2,3-二羥基-1,4-雙[雙(3,5-二乙基苯基)膦]。
比較性二膦1C
:2,3-O
-亞異丙基-2,3-二羥基-1,4-雙[雙(苯基)膦],即DIOP。
比較性二膦1D
:2,3-O
-亞異丙基-2,3-二羥基-1,4-雙[雙(4-甲基苯基)膦]丁烷。
比較性二膦1E
:2,3-O
-亞異丙基-2,3-二羥基-1,4-雙[雙(3,5-二甲基-4-甲氧基苯基)膦]丁烷。
比較性二膦1F
:2,3-O
-亞異丙基-2,3-二羥基-1,4-雙[雙(4-氯苯基)膦]丁烷。
比較性二膦1G
:2,3-O
-亞異丙基-2,3-二羥基-1,4-雙[雙(3,5-二(三氟甲基)苯基)膦]丁烷。
比較性二膦1H
:2,3-O
-亞異丙基-2,3-二羥基-1,4-雙[雙(3,5-二(第三丁基)苯基)膦]丁烷。
比較性二膦1I
:2,3-O
-亞異丙基-2,3-二羥基-1,4-雙[雙(2-萘次甲基)膦]丁烷。
比較性二膦1J
:2,3-O
-亞異丙基-2,3-二羥基-1,4-雙[雙(2,4,6-三甲基苯基)膦]丁烷。
根據以下步驟使用二膦1A-1J將烯丙醇氫甲醯化:在100 mL之Parr高壓釜中,將溶於乾燥除氣之甲苯中的所欲二膦(2當量,或8.6×10-5
莫耳)溶液加入[Rh(CO)2
(acac)](1當量,或4.3×10-5
莫耳)中。以1:1之CO/H2
混合物沖洗該溶液三次,然後以CO/H2
混合物將其加壓至180 psig。然後將高壓釜攪拌並加熱至65℃,注入烯丙醇(3.5 mL),並以CO/H2
混合物將高壓釜加壓至200 psig。將高壓釜維持於200 psig之恆定壓力下,並監測反應中氣體的吸收。當無進一步之氣體吸收時,將高壓釜冷卻並減壓。使所得之溶液經由氣相層析法分析後以決定反應的產物。該反應產生HBA、HMPA和C3
產物(正丙醇和丙醛)。
顯示於表1中之結果說明了本發明之2,3-O
-亞異丙基-2,3-二羥基-1,4-雙[雙(3,5-二-正-烷基苯基)膦]丁烷,較其他比較性二膦配位基而言,係出乎預期地產生明顯較高之HBA:HMPA(l:b)比例。
Claims (12)
- 一種製造4-羥丁醛的方法,其包括在存有溶劑和一種包括銠錯合物和2,3-O -亞異丙基-2,3-二羥基-1,4-雙[雙(3,5-二-正-烷基苯基)膦]丁烷之觸媒系統中,使烯丙醇與一氧化碳和氫氣反應。
- 根據申請專利範圍第1項的方法,其中該觸媒系統包括銠錯合物和2,3-O -亞異丙基-2,3-二羥基-1,4-雙[雙(3,5-二甲基苯基)膦]丁烷。
- 根據申請專利範圍第1項的方法,其中該觸媒系統包括銠錯合物和2,3-O -亞異丙基-2,3-二羥基-1,4-雙[雙(3,5-二乙基苯基)膦]丁烷。
- 根據申請專利範圍第1項的方法,其中該溶劑係選自由C5 -C20 之脂肪族碳氫化合物、C6 -C12 之芳香族碳氫化合物、醚、醇及其混合物所組成的群組中。
- 根據申請專利範圍第1項的方法,其中該溶劑係選自由甲苯、環己烷、甲基第三丁基醚及其混合物所組成的群組中。
- 根據申請專利範圍第1項的方法,其中該銠錯合物包括銠及選自由氫化物、羰基、三烷基或三芳基膦、二膦、環戊二烯基、2,4-烷二酸鹽(alkanedionate)、以及其混合物所組成的群組中之配位基。
- 根據申請專利範圍第1項的方法,其中該反應係在45℃至85℃之溫度範圍內以及在30至400 psig之壓力範圍內進行。
- 根據申請專利範圍第1項的方法,其中該觸媒系統亦可額外包括單膦化合物。
- 根據申請專利範圍第8項的方法,其中該單膦化合物為三苯基膦。
- 根據申請專利範圍第1項的方法,其中在液相中之一氧化碳濃度係維持在高於4 mmols/升。
- 根據申請專利範圍第1項的方法,其進一步包括在存有氫化觸媒下使4-羥丁醛氫化而形成1,4-丁二醇。
- 根據申請專利範圍第11項的方法,其中該氫化觸媒為鎳觸媒。
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US7655821B1 (en) | 2008-11-25 | 2010-02-02 | Lyondell Chemical Technology, L.P. | Direct hydrocarbonylation process |
US7612241B1 (en) | 2009-03-23 | 2009-11-03 | Lyondell Chemical Technology, L.P. | Hydroformylation process |
US20100292514A1 (en) * | 2009-05-13 | 2010-11-18 | White Daniel F | Hydroformylation process |
US7790932B1 (en) | 2009-12-21 | 2010-09-07 | Lyondell Chemical Technology, L.P. | Hydroformylation process |
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