CN102428062A - 加氢甲酰化方法 - Google Patents
加氢甲酰化方法 Download PDFInfo
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- CN102428062A CN102428062A CN2010800210300A CN201080021030A CN102428062A CN 102428062 A CN102428062 A CN 102428062A CN 2010800210300 A CN2010800210300 A CN 2010800210300A CN 201080021030 A CN201080021030 A CN 201080021030A CN 102428062 A CN102428062 A CN 102428062A
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- diphosphine
- isopropylidene
- butane
- phosphino
- dihydroxyl
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- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000007037 hydroformylation reaction Methods 0.000 title description 20
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims abstract description 56
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000010948 rhodium Substances 0.000 claims abstract description 28
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 27
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 27
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001273 butane Substances 0.000 claims abstract description 23
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 32
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 24
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 21
- -1 phosphinomethyl Chemical group 0.000 claims description 20
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- DGXRZJSPDXZJFG-UHFFFAOYSA-N docosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCCCC(O)=O DGXRZJSPDXZJFG-UHFFFAOYSA-N 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- JTMCAHGCWBGWRV-UHFFFAOYSA-N 3-hydroxy-2-methylpropanal Chemical compound OCC(C)C=O JTMCAHGCWBGWRV-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- PIAOXUVIBAKVSP-UHFFFAOYSA-N γ-hydroxybutyraldehyde Chemical compound OCCCC=O PIAOXUVIBAKVSP-UHFFFAOYSA-N 0.000 abstract 2
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 abstract 1
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 abstract 1
- 239000003446 ligand Substances 0.000 description 10
- NBBJYMSMWIIQGU-UHFFFAOYSA-N propionic aldehyde Natural products CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-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
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- ZGEZPSPEVXDOMG-UHFFFAOYSA-N lithium;phosphane Chemical compound [Li].P ZGEZPSPEVXDOMG-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- CXNIUSPIQKWYAI-UHFFFAOYSA-N xantphos Chemical compound C=12OC3=C(P(C=4C=CC=CC=4)C=4C=CC=CC=4)C=CC=C3C(C)(C)C2=CC=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 CXNIUSPIQKWYAI-UHFFFAOYSA-N 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
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- VOAXSDYMVCZQHO-UHFFFAOYSA-N 4-phosphanylbutylphosphane Chemical compound PCCCCP VOAXSDYMVCZQHO-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
- PXLURWFICFXLQT-UHFFFAOYSA-N P.P.CCCC Chemical compound P.P.CCCC PXLURWFICFXLQT-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 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
- 238000007872 degassing Methods 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
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- MUYMYVQSDKODSB-UHFFFAOYSA-N formaldehyde;rhodium;triphenylphosphane Chemical compound [Rh].O=C.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 MUYMYVQSDKODSB-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 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
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000005490 tosylate group Chemical group 0.000 description 1
- WHAFDJWJDDPMDO-UHFFFAOYSA-N trimethyl(phenyl)phosphanium Chemical compound C[P+](C)(C)C1=CC=CC=C1 WHAFDJWJDDPMDO-UHFFFAOYSA-N 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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- 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
- B01J31/2414—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 comprising aliphatic or saturated rings
-
- 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
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- 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
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- 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
- C07C45/50—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 by oxo-reactions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/17—Saturated compounds containing keto groups bound to acyclic carbon atoms containing hydroxy groups
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- 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
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- 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
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- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0269—Complexes comprising ligands derived from the natural chiral pool or otherwise having a characteristic structure or geometry
- B01J2531/0272—Complexes comprising ligands derived from the natural chiral pool or otherwise having a characteristic structure or geometry derived from carbohydrates, including e.g. tartrates or DIOP
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Abstract
描述了一种4-羟基丁醛的制备方法。该方法包括在溶剂和包含铑络合物和二膦的催化剂的存在下使烯丙醇与一氧化碳和氢气的混合物反应。所述二膦为反式-1，2-双(双(3，4-二正烷基苯基)膦基甲基)环丁烷和/或2，3-O-异亚丙基-2，3-二羟基-1，4-双[双(3，4-二正烷基苯基)膦基]丁烷。相较于3-羟基-2-甲基丙醛，该方法得到高收率的4-羟基丁醛。
Description
技术领域
本发明涉及一种将烯丙醇加氢甲酰化制备4-羟基丁醛的方法。
背景技术
烯丙醇的加氢甲酰化是公知的和工业上实践的方法。参见，例如，美国专利号4,064,145、4,215,077、4,238,419、4,678,857和5,290,743。在加氢甲酰化反应中，烯丙醇与CO/H2气体混合物在催化剂的存在下反应生成4-羟基丁醛(HBA)。该HBA然后可例如通过水萃取与催化剂分离，并氢化生成1，4-丁二醇(BDO)。参见美国专利号5,504,261。
多种催化剂体系已用于该加氢甲酰化反应，最著名的是与膦配体一同使用的铑络合物(参见，例如美国专利号4,064,145、4,238,419和4,567,305)。通常采用的膦配体为三取代的膦例如三苯基膦。
加氢甲酰化方法的一个缺点是除了需要的HBA直链产物外，还形成其他共产物或副产物。烯丙醇加氢甲酰化通常产生一些3-羟基-2-甲基丙醛(HMPA)支化共产物和C3副产物如正丙醇和丙醛。虽然HMPA可加氢制备有用的材料2-甲基-1，3-丙二醇(MPD)，但该MPD共产物降低了BDO的产率。C3副产物的生成有效地反映了该方法的另一种产率损失，这对于该方法的经济性有严重的不利影响。
为提高BDO产率，人们继续研究以改进加氢甲酰化方法并降低不那么需要的共产物/副产物。美国专利号6,127,584公开了具有至少2个甲基的三烷基膦配体的使用导致HBA∶HMPA之比增加。已发现二膦配体的使用提高了HBA∶HMPA之比。本领域中已知使用铑络合物催化剂和二膦配体例如DIOP、XANTPHOS或反式-1，2-双(二苯基膦基甲基)环丁烷来加氢甲酰化烯丙醇，尤其是日本公开特许公报06-279345及06-279344和美国专利号4,306,087。美国专利号6,225,509公开了当使用含铑络合物和配体例如DIOP的催化剂时，将CO在反应液中的浓度维持在高于大约4.5mmols/升降低了不需要的C3共产物生成。另外，美国专利号7,271,295和7,279,606分别公开了2，3-O-异亚丙基-2，3-二羟基-1，4-双[双(3，5-二正烷基苯基)膦基]丁烷配体或反式-1，2-双(双(3，5-二正烷基苯基)膦甲基)环丁烷配体的使用。
总之，需要新的加氢甲酰化烯丙醇以制备4-羟基丁醛的方法。特别有价值的方法可得到高的4-羟基丁醛与3-羟基-2-甲基丙醛比值。
发明概述
本发明是一种方法，包括烯丙醇与一氧化碳和氢气在溶剂和催化剂的存在下反应生成4-羟基丁醛。所述催化剂包含铑络合物和反式-1，2-双(双(3，4-二正烷基苯基)膦甲基)环丁烷和/或2，3-O-异亚丙基-2，3-二羟基-1，4-双[双(3，4-二正烷基苯基)膦基]丁烷。本发明也包括催化剂。本发明令人吃惊地得到高的4-羟基丁醛与3-羟基-2-甲基丙醛比值。
发明详述
本发明的方法包括在溶剂和催化剂的存在下加氢甲酰化烯丙醇。本发明的催化剂包括铑络合物和二膦配体。所述二膦为反式-1，2-双(双(3，4-二正烷基苯基)膦甲基)环丁烷和/或2，3-O-异亚丙基-2，3-二羟基-1，4-双[双(3，5-二正烷基苯基)膦基]丁烷。
反式-1，2-双(双(3，4-二正烷基苯基)膦甲基)环丁烷具有如下化学式：
其中每一个R独立为正烷基基团。优选地，R为甲基、乙基或丙基。
所述反式-1，2-双(双(3，4-二正烷基苯基)膦甲基)环丁烷二膦配体最优选反式-1，2-双(双(3，4-二甲基苯基)膦甲基环丁烷或反式-1，2-双(双(3，4-二乙基苯基)膦甲基)环丁烷。
2，3-O-异亚丙基-2，3-二羟基-1，4-双[双(3，4-二正烷基苯基)膦基]丁烷具有如下化学式：
其中每一个R独立为正烷基基团。优选地，R为甲基、乙基或丙基。
所述2，3-O-异亚丙基-2，3-二羟基-1，4-双[双(3，4-二正烷基苯基)膦基]丁烷二膦配体最优选2，3-O-异亚丙基-2，3-二羟基-1，4-双[双(3，4-二甲基苯基)膦基]丁烷或2，3-O-异亚丙基-2，3-二羟基-1，4-双[双(3，4-二乙基苯基)膦基]丁烷。
所述二膦配体可用任何可能的方法制备。例如，2，3-O-异亚丙基-2，3-二羟基-1，4-双[双(3，4-二正烷基苯基)膦基]丁烷可通过2，2-二甲基-4，5-双[(甲苯磺酰氧基甲基)甲基]-1，3-二氧戊环与二(3，4-二正烷基苯基)膦锂反应制备。反式-1，2-双(双(3，4-正烷基苯基)膦基甲基)环丁烷可通过反式-1，2-环丁烷二甲醇，双(甲苯磺酸盐)与二(3，4-二正烷基苯基)膦锂反应制备。
本发明的催化剂还包含铑络合物。合适的铑络合物含有与配体基团连接的铑。优选所述铑络合物在溶剂中是可溶的。对于与所述铑络合物连接的配体的选择没有特别的限制。例如，合适的配体包括氢化物、羰基、取代和未取代的环戊二烯基、2，4-链烷二酸根、三烷基膦、三芳基膦、二膦及其混合物。特别优选的配体包括羰基、乙酰丙酮化物(2，4-戊二酸根)、三苯基膦及其混合物。优选的铑配合物实例包括(乙酰丙酮)二羰基铑和三(三苯基膦)铑羰基氢化物。
在用于加氢甲酰化反应之前，所述铑络合物可与所述反式-1，2-双(双(3，4-二正烷基苯基)膦基甲基)环丁烷或2，3-O-异亚丙基-2，3-二羟基-1，4-双[双(3，4-二正烷基苯基)膦基]丁烷二磷配体预先结合以使得双(双(3，4-二正烷基苯基)膦基甲基)环丁烷或2，3-O-异亚丙基-2，3-二羟基-1，4-双[双(3，4-二正烷基苯基)膦基]丁烷形成铑络合物的一部分，或它可以单独加入。然而，优选所述铑络合物与反式-1，2-双(双(3，4-二正烷基苯基)膦基甲基)环丁烷或2，3-O-异亚丙基-2，3-二羟基-1，4-双[双(3，4-二正烷基苯基)膦基]丁烷分开加入。二膦配体∶铑络合物的摩尔比优选在0.5∶1至5∶1范围内。
尽管并非必需，所述催化剂可另外包含单膦化合物。所述单膦化合物还可以是与所述铑络合物结合的任何膦配体。所述单膦化合物为以下化学式表示的三取代膦：
(R1)3P
其中R1为芳基或烷基。合适的脂族R1基团包括甲基、乙基、正丁基、仲丁基、辛基和癸基。合适的芳族R1基团包括苯基、甲苯基和萘基。R1基团可相同或不同，但优选相同。优选地，该单膦为三取代芳基膦。更优选地，该单膦为三苯基膦或三甲苯基膦。三苯基膦是特别优选的。
本发明的方法也需要反应溶剂。一般的溶剂是能够溶解所述铑配合物且对加氢甲酰化步骤中产生的羟基醛不具有反应性的那些。合适的溶剂包括在水中具有非常低或最小溶解度的任何有机溶剂。优选的溶剂包括C5-C20脂族烃、C6-C20芳族烃、醇、醚及其混合物。特别优选的溶剂包括甲苯、环己烷、甲基叔丁基醚及其混合物。
用于所述加氢甲酰化步骤的一般的反应条件是温和的，以利于生成直链的4-羟基丁醛(HBA)而不是支化的3-羟基-2-甲基丙醛(HMPA)反应产物。反应条件优选为在大约20至120℃以及20至600psig压力范围内，更优选为大约45至85℃及30至400psig，且最优选50至80℃及40至300psig。CO∶H2摩尔比一般为大约1∶1，尽管该比例可相当大地变化。CO的分压一般在5至100psig范围内。氢气的分压一般在40至200psig范围内。在这些条件下进行该反应直到绝大多数烯丙醇已经反应，如60至99.9％，产物大部分为4-羟基丁醛，以及一些支化的反应产物。反应时间长短不是关键的，但通常0.5至4小时的反应时间是足够的。
优选地，基于待进料的反应溶剂，烯丙醇在溶剂中的起始浓度为5至40重量百分比；更优选地，可以使用5至10重量百分比的较低浓度。
优选地，进行烯丙醇的加氢甲酰化使得CO在液相中的浓度([CO]液)在加氢甲酰化期间维持在高于4mmols/升(0.004M)。[CO]液的值在美国专利号6,225,509中有定义，其说法通过引用方式并入本文。优选地，液相氢∶一氧化碳摩尔比为10∶1至1∶2，优选5∶1至1∶2。
加氢甲酰化步骤之后，优选在萃取容器中通过水萃取使HBA产物与溶剂和催化剂分离。水萃取方法为本领域公知的，且可通过任何适宜的设备实施，例如混合器-沉降器、填料式或板式萃取塔、旋转盘接触器，或送至沉降槽使该混合物分离为水相和有机相。HBA，和任何HMPA，在水(含水)相中保持溶解，并与溶剂(有机)相分开。
所述4-羟基丁醛(和任何3-羟基2-甲基丙醛)反应产物优选在加氢催化剂存在下进行额外的4-羟基丁醛加氢步骤制备1，4-丁二醇(BDO)。将氢气加入到用于加氢的反应容器中。合适的加氢催化剂包括任何第VIII族金属，如镍、钴、钌、铂和钯，以及铜、锌和铬及其混合物和合金。特别优选的是镍催化剂。最优选的是Raney
镍型和固定床镍催化剂。
加氢反应条件优选在60至200℃和200至1000psig压力范围内，更优选为80至140℃和300至1000psig。通常1至10小时的反应时间是适当的。加氢反应过程中，生成BDO和MPD，此时基本上保持高的直链与支链产物之比，还有其他少量共产物/副产物。
以下实施例仅用于说明本发明。本领域技术人员能够认识到在本发明主旨和权利要求范围内的多种变化。
实施例1：二膦的制备
1A、1B、1C、1D和1E：按照如下所述制备以下通式的二膦1A、1B、1C、1D和1E。
在氩气下将2，2-二甲基-4，5-双[(甲苯磺酰氧基甲基)甲基]-1，3-二氧戊环在干燥/脱气的THF中的溶液(1当量，1.73g，3.7×10-3摩尔的二氧戊环在50mlTHF中)逐滴加入到适量的二芳基膦锂(参见上述化学式)在干燥/脱气的THF中的溶液(2.3当量，在100ml THF中)。加热该混合物回流2小时，然后冷却，并在减压下除去溶剂。将剩余的固体重新溶解在二氯甲烷中，通过二氧化硅床过滤，并在减压下除去溶剂以得到2，3-O-异亚丙基-2，3-二羟基-1，4-双(双芳基膦)丁烷。
二膦1A：2，3-O-异亚丙基-2，3-二羟基-1，4-双[双(3，4-二甲基苯基)膦基]丁烷。
对比性二膦1B：2，3-O-异亚丙基-2，3-二羟基-1，4-双[双(3，5-二甲基苯基)膦基]丁烷。
对比性二膦1C：2，3-O-异亚丙基-2，3-二羟基-1，4-双[双(苯基)膦基]丁烷，即已知的DIOP。
对比性二膦1D：2，3-O-异亚丙基-2，3-二羟基-1，4-双[双(3，5-二甲基-4-甲氧基苯基)膦基]丁烷。
对比性二膦1E：2，3-O-异亚丙基-2，3-二羟基-1，4-双[双(2-萘基)膦基]丁烷。
对比性二膦1F：2，3-O-异亚丙基-2，3-二羟基-1，4-双[双(4-甲基苯基)膦基]丁烷。
对比性二膦1G：2，3-O-异亚丙基-2，3-二羟基-1，4-双[双(2，4，6-三甲基苯基)膦基]丁烷。
实施例2：使用二膦的加氢甲酰化反应
根据以下步骤使用二膦1A-1E对烯丙醇进行加氢甲酰化：
将需要的二膦(2当量或8.6×10-5摩尔)在干燥脱气的甲苯(15g)中的溶液加入到在100ml Parr高压釜中的[Rh(CO)2(acac)](1当量或4.3×10-5摩尔)中。用1∶1CO/H2混合物冲洗该溶液三次，然后用该CO/H2混合物加压至180psig。然后在搅拌下将高压釜加热至65℃，注入烯丙醇(3.5ml)，并用CO/H2混合物将高压釜加压至200psig。该高压釜维持200psig的恒定压力，并监测该反应的气体吸收。当没有进一步的气体吸收时，冷却高压釜并卸压。用气相色谱分析所得反应溶液以确定反应产物。该反应产生HBA、HMPA、和C3产物(正丙醇和丙醛)。
表1：二膦对比
*对比例
Claims (15)
1.一种制备4-羟基丁醛的方法，包括在溶剂和催化剂的存在下使烯丙醇与一氧化碳和氢气反应，催化剂包含铑络合物和选自反式-1，2-双(双(3，4-二正烷基苯基)膦基甲基)环丁烷、2，3-O-异亚丙基-2，3-二羟基-1，4-双[双(3，4-二正烷基苯基)膦基]丁烷及其混合物的二膦。
2.如权利要求1所述的方法，其中所述二膦为反式-1，2-双(双(3，4-二甲基苯基)膦基甲基)环丁烷。
3.如权利要求1所述的方法，其中所述二膦为反式-1，2-双(双(3，4-二乙基苯基)膦基甲基)环丁烷。
4.如权利要求1所述的方法，其中所述二膦为2，3-O-异亚丙基-2，3-二羟基-1，4-双[双(3，4-二甲基苯基)膦基]丁烷。
5.如权利要求1所述的方法，其中所述二膦为2，3-O-异亚丙基-2，3-二羟基-1，4-双[双(3，4-二乙基苯基)膦基]丁烷。
6.如权利要求1所述的方法，其中所述溶剂选自C5-C20脂族烃、C6-C12芳族烃、醚、醇及其混合物。
7.如权利要求1所述的方法，其中所述溶剂选自由甲苯、环己烷、甲基叔丁基醚及其混合物。
8.如权利要求1所述的方法，其中所述铑络合物包括铑和选自氢化物、羰基、三烷基膦、三芳基膦、二膦、环戊二烯基、2，4-链烷二酸根及其混合物的配体。
9.如权利要求1所述的方法，其中所述催化剂进一步包括单膦化合物。
10.如权利要求1所述的方法，进一步包括在加氢催化剂存在下氢化4-羟基丁醛形成1，4-丁二醇。
11.一种催化剂，包括铑络合物和选自反式-1，2-双(双(3，4-二正烷基苯基)膦基甲基)环丁烷、2，3-O-异亚丙基-2，3-二羟基-1，4-双[双(3，4-二正烷基苯基)膦基]丁烷及其混合物的二膦。
12.如权利要求11所述的催化剂，其包括铑络合物和反式-1，2-双(双(3，4-二甲基苯基)膦基甲基)环丁烷。
13.如权利要求11所述的催化剂，其包括铑络合物和反式-1，2-双(双(3，4-二乙基苯基)膦基甲基)环丁烷。
14.如权利要求11所述的催化剂，其包括铑络合物和2，3-O-异亚丙基-2，3-二羟基-1，4-双[双(3，4-二甲基苯基)膦基]丁烷。
15.如权利要求11所述的催化剂，其包括铑络合物和2，3-O-异亚丙基-2，3-二羟基1，4-双[双(3，4-二乙基苯基)膦基]丁烷。
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- 2010-04-29 WO PCT/US2010/001257 patent/WO2010132087A1/en active Application Filing
- 2010-04-29 ES ES10720050T patent/ES2430224T3/es active Active
- 2010-04-29 SG SG2011081601A patent/SG175908A1/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111801312A (zh) * | 2018-02-26 | 2020-10-20 | 利安德化学技术有限公司 | 由甘油制备的烯丙醇经加氢甲酰化产生bdo |
| CN111801312B (zh) * | 2018-02-26 | 2022-03-04 | 利安德化学技术有限公司 | 由甘油制备的烯丙醇经加氢甲酰化产生bdo |
| CN109553594A (zh) * | 2018-12-25 | 2019-04-02 | 山东新和成药业有限公司 | 一种四氢呋喃-3-甲醛的制备方法 |
| CN109553594B (zh) * | 2018-12-25 | 2020-12-18 | 山东新和成药业有限公司 | 一种四氢呋喃-3-甲醛的制备方法 |
| CN112457165A (zh) * | 2019-09-06 | 2021-03-09 | 南京延长反应技术研究院有限公司 | 一种烯丙醇加氢制备1，4-丁二醇的强化系统及工艺 |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2761037A1 (en) | 2010-11-18 |
| ES2430224T3 (es) | 2013-11-19 |
| WO2010132087A1 (en) | 2010-11-18 |
| KR20120022926A (ko) | 2012-03-12 |
| BRPI1010643A2 (pt) | 2016-06-07 |
| SG175908A1 (en) | 2011-12-29 |
| EP2429978A1 (en) | 2012-03-21 |
| US20100292514A1 (en) | 2010-11-18 |
| BRPI1010643B1 (pt) | 2018-02-14 |
| EP2429978B1 (en) | 2013-09-11 |
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