CN101652179B - 加氢甲酰化方法 - Google Patents
加氢甲酰化方法 Download PDFInfo
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- CN101652179B CN101652179B CN2008800102101A CN200880010210A CN101652179B CN 101652179 B CN101652179 B CN 101652179B CN 2008800102101 A CN2008800102101 A CN 2008800102101A CN 200880010210 A CN200880010210 A CN 200880010210A CN 101652179 B CN101652179 B CN 101652179B
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- cyclobutane
- phosphinomethyl
- rhodium complex
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- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000007037 hydroformylation reaction Methods 0.000 title description 20
- 239000010948 rhodium Substances 0.000 claims abstract description 30
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 29
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims abstract description 28
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 28
- PIAOXUVIBAKVSP-UHFFFAOYSA-N γ-hydroxybutyraldehyde Chemical compound OCCCC=O PIAOXUVIBAKVSP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 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 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 4
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims description 42
- -1 phosphinomethyl Chemical group 0.000 claims description 37
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 35
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 claims description 29
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000005984 hydrogenation reaction Methods 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 239000007868 Raney catalyst Substances 0.000 claims description 3
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical group [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- JTMCAHGCWBGWRV-UHFFFAOYSA-N 3-hydroxy-2-methylpropanal Chemical compound OCC(C)C=O JTMCAHGCWBGWRV-UHFFFAOYSA-N 0.000 abstract 1
- NBBJYMSMWIIQGU-UHFFFAOYSA-N propionic aldehyde Natural products CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 11
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003446 ligand Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical group CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000004862 dioxolanes Chemical class 0.000 description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 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 2
- 150000003003 phosphines Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical group CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid 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
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 208000035126 Facies Diseases 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
- 150000004808 allyl alcohols Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 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
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 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
- 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
- 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
- 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
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000003944 tolyl 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
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
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- 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
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- 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
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- 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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- 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
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Abstract
描述了生产4-羟基丁醛的方法。所述方法包括在溶剂和催化剂体系的存在下使烯丙醇与一氧化碳和氢气的混合物反应，所述催化剂体系包含铑络合物和反式-1，2-双(双(3，5-二正烷基苯基)膦基甲基)环丁烷。与3-羟基-2-甲基丙醛相比，所述方法给出了4-羟基丁醛的高产率。
Description
发明领域
本发明涉及将烯丙醇加氢甲酰化以生产4-羟基丁醛的方法。所述方法产生出乎意料地高的4-羟基丁醛：3-羟基-2-甲基丙醛(直链：支化)产物之比。
发明背景
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以生成4-羟基丁醛(HBA)。该HBA然后可以例如通过水萃取与催化剂分开，并加氢以生成1，4-丁二醇(BDO)。参见美国专利号5,504,261。
已经采用了多种催化剂体系用于该加氢甲酰化反应，最特别的是与膦配体一起使用的铑络合物(参见，例如，美国专利号4,064,145、4,238,419和4,567,305)。通常采用的膦配体是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想要的HBA直链产物外，还生成其它共产物或副产物。烯丙醇的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副产物例如正丙醇和丙醛。尽管HMPA可以被加氢以产生有用的物质1，3-甲基丙二醇(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过程中的另一产率损失，这会对于过程经济性有严重的不利影响。
为了增加BDO产率，持续研究以改进加氢甲酰化方法并降低不那么想要的共产物/副产物。美国专利号6,127,584公开了使用具有至少2个甲基的三烷基膦配体导致增加的HBA：HMPA之比。还发现使用二膦配体改进了HBA：HMPA之比。使用铑络合物催化剂和二膦配体例如DIOP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在本领域中，特别是在日本Kokai号06-279345和06-279344和美国专利号4,306,087中是已知的。美国专利号6,225,509公开了将CO在反应液体中的浓度维持在高于约4.5毫摩尔/升降低了在使用由铑络合物和配体例如DIOP组成的催化剂时不想要的C3共产物的生成。此外，共同未决的美国专利申请序列号11/580,510公开了使用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]丁烷配体导致与3-羟基-2-甲基丙醛相比4-羟基丁醛的产率非常高。
总之，需要用来加氢甲酰化烯丙醇以生产4-羟基丁醛的新方法。特别有价值的方法将导致高的4-羟基丁醛(HBA)与3-羟基-2-甲基丙醛(HMPA)之比。
发明概述
本发明是一种方法，该方法包括在溶剂和催化剂体系的存在下使烯丙醇与一氧化碳和氢气反应以生产4-羟基丁醛。所述催化剂体系包含铑络合物和反式-1，2-双(双(3，5-二正烷基苯基)膦基甲基)环丁烷。本发明令人惊讶地导致高的4-羟基丁醛产物与3-羟基-2-甲基丙醛之比。
发明详述
本发明的方法包括在溶剂和催化剂体系的存在下加氢甲酰化烯丙醇。本发明的催化剂体系包含铑络合物和反式-1，2-双(双(3，5-二正烷基苯基)膦基甲基)环丁烷。反式-1，2-双(双(3，5-二正烷基苯基)膦基甲基)环丁烷具有化学式：
其中R是正烷基。优选地，R是甲基、乙基或丙基。
所述二膦配体最优选是反式-1，2-双(双(3，5-二甲基苯基)膦基甲基)环丁烷或反式-1，2-双(双(3，5-二乙基苯基)膦基甲基)环丁烷。
所述反式-1，2-双(双(3，5-二正烷基苯基)膦基甲基)环丁烷可以通过任何可能的方法来制备。例如，它可以通过反式-1，2-环丁烷二甲醇、双(甲苯磺酸盐)与锂二(3，5-二正烷基苯基)膦的反应来制备。
本发明的催化剂体系还包含铑络合物。适宜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所述溶剂中是可溶的。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，适宜的配体包括氢、羰基、取代的和未取代的环戊二烯基、2，4-链烷双酸根(2，4-alkanedionates)、三烷基膦或三芳基膦、二膦和它们的混合物。特别优选的配体包括羰基、乙酰丙酮化物(2，4-戊二酸根(2，4-pentanedionate))、三苯基膦和它们的混合物。优选的铑络合物的实例包括(乙酰丙酮)二羰基铑和三(三苯基膦)铑羰基氢化物。
所述铑络合物可以在用于加氢甲酰化反应之前与所述反式-1，2-双(双(3，5-二正烷基苯基)膦基甲基)环丁烷预先结合以使得双(双(3，5-二正烷基苯基)膦基甲基)环丁烷配体形成该铑络合物的一部分，或者它可以被单独加入。然而，优选所述铑络合物与所述反式-1，2-双(双(3，5-二正烷基苯基)膦基甲基)环丁烷分开加入。所述反式-1，2-双(双(3，5-二正烷基苯基)膦基甲基)环丁烷∶铑络合物的摩尔比优选为0.5∶1至5∶1。
尽管并非必需，所述催化剂体系可以额外地包含单膦化合物。所述单膦化合物还可以是可与所述铑络合物结合的任何膦配体。所述单膦化合物是可用以下化学式表示的三取代的膦：
(R1)3P
其中R1是芳基或烷基。适宜的脂族R1基团包括甲基、乙基、正丁基、仲丁基、辛基和癸基。适宜的芳族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，所述单膦是三取代的芳基膦。更优选地，所述单膦是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络合物且对于加氢甲酰化步骤中产生的羟基醛不具有反应性的那些。适宜的溶剂包括在水中具有非常低或最小的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、醚和它们的混合物。特别优选的溶剂包括甲苯、环己烷、甲基叔丁基醚和它们的混合物。
用于所述加氢甲酰化步骤的一般的反应条件是温和的以有利于生成直链的4-羟基丁醛(HBA)而非支化的3-羟基-2-甲基丙醛(HMPA)反应产物。反应条件优选为约20-120℃和约20-600psig的压力，更优选为约45-85℃和30-400psig，和最优选为约50-80℃和40-300psig。CO∶H2摩尔比一般为约1∶1，尽管该比例可以相当大地变化。CO的分压一般为5-100psig。氢气的分压一般为40-200psig。在这些条件下进行该反应直至绝大多数烯丙醇(例如60-99.9％)已经反应，产物大部分是4-羟基丁醛，有一些是支化的反应产物。反应时间的量不是关键的，但通常0.5-4小时的反应时间是足够的。
优选地，基于待进料的反应溶剂，烯丙醇在该溶剂中的起始浓度为约5-40wt％；更优选地，可以使用5-10wt％的更低的浓度。
优选地，这样实施烯丙醇的加氢甲酰化以使得CO在液相中的浓度([CO]液)在加氢甲酰化过程中维持在高于4毫摩尔/升(0.004M)。[CO]液的值在美国专利号6,225,509中有定义。优选地，液相氢∶一氧化碳摩尔比为10∶1至约1∶2，更优选5∶1至约1∶2。
加氢甲酰化步骤之后，优选通过在萃取容器中进行水萃取来将HBA产物与所述溶剂和催化剂体系分开。水萃取方法是本领域公知的，并且可以通过任何适宜的设备来实施，例如混合器-沉降器、填料萃取塔或板式萃取塔、旋转盘接触器，或送至沉降槽来将该混合物分离成水相和有机相。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)反应产物优选经过额外的在加氢催化剂的存在下对4-羟基丁醛进行加氢的步骤以产生1，4-丁二醇(BDO)。将氢气加入到用于该加氢的反应容器中。适宜的加氢催化剂包括任何VIII族金属，例如镍、钴、钌、铂和钯，以及铜、锌和铬和它们的混合物和合金。特别优选的是镍催化剂。最优选的是Raney型镍和固定床镍催化剂。
所述加氢反应条件优选为约60-200℃和约200-1000psig的压力，更优选约80-140℃和300-1000psig。通常1-10小时的反应时间是适当的。在该加氢反应过程中，生成BDO和MPD，而高的直链与支化产物之比基本上保留，还有其它低级共产物/副产物。
以下实施例仅举例说明本发明。本领域技术人员将意识到在本发明的主旨和权利要求的范围内的许多变化。
实施例1：二膦的制备
1A、1B和1C：如下所述制备以下通式的二膦1A、1B和1C。
在氩气下将反式-1，2-环丁烷二甲醇、双(甲苯磺酸盐)在干燥/脱气的THF中的溶液(1当量，1.73g，3.7x10-3摩尔的二氧戊环在50mL THF中)逐滴加入到适量的锂二芳基膦(见以上化学式)在干燥/脱气的THF中的溶液(2.3当量，在100mL THF)中。在回流下加热该混合物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反式-1，2-双(二芳基膦基甲基)环丁烷。
二膦1A：反式-1，2-双(双(3，5-二甲基苯基)膦基甲基)环丁烷。
对比性的二膦1B：反式-1，2-双(双(4-甲基苯基)膦基甲基)环丁烷。
对比性的二膦1C：反式-1，2-双(二苯基膦基甲基)环丁烷。
1D、1E和1F：如下所述制备以下通式的二膦1D、1E和1F。
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，3.7x 10-3摩尔的二氧戊环在50mL THF中)逐滴加入到适量的锂二芳基膦(见以上化学式)在干燥/脱气的THF中的溶液(2.3当量，在100mL THF)中。在回流下加热该混合物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(二芳基膦基)丁烷。
对比性的二膦1D：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。
对比性的二膦1E：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。
对比性的二膦1F：2，3-O-异亚丙基-2，3-二羟基-1，4-双[双(苯基)膦基]，也称作DIOP。
实施例2：使用二膦的加氢甲酰化反应
根据以下程序使用二膦配体1A-1F来加氢甲酰化烯丙醇：
将想要的二膦(2当量或8.6×10-5摩尔)在干燥脱气的甲苯(15g)中的溶液加入到位于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。然后在搅拌下将该高压釜加热至65℃，注入烯丙醇(3.5mL)，并用该CO/H2混合物将该高压釜加压至200psig。该高压釜保持在200psig的恒定压力下，并监测该反应的气体吸收。当没有进一步的气体吸收时，冷却该高压釜并卸压。用气相色谱分析所得到的溶液以确定该反应的产物。该反应产生HBA、HMPA和C3产物(正丙醇和丙醛)。
示于表1中的结果表明，本发明的反式-1，2-双(双(3，5-二正烷基苯基)膦基甲基)环丁烷出乎意料地导致比任何其它对比性的二膦显著更高的HBA∶HMPA(1∶b)之比。
表1：二膦对比
| 二膦 | 转化率(％) | HBA(％) | HMPA(％) | C3(％) | 1∶b比例 |
| 1A | 99.50 | 91.0 | 8.3 | 0.2 | 11.0 |
| 1B* | 99.30 | 89.3 | 9.8 | 0.2 | 9.1 |
| 1C* | 99.94 | 88.6 | 10.8 | 0.1 | 8.2 |
| 1D* | 99.66 | 89.8 | 9.4 | 0.2 | 9.5 |
| 1E* | 99.98 | 86.5 | 11.3 | 0.2 | 7.7 |
| 1F* | 99.75 | 86.2 | 11.7 | 0.2 | 7.4 |
*对比例
Claims (13)
1.生产4-羟基丁醛的方法，包括在溶剂和催化剂体系的存在下使烯丙醇与一氧化碳和氢气反应，所述催化剂体系包含铑络合物和反式-1，2-双(双(3，5-二正烷基苯基)膦基甲基)环丁烷，所述反式-1，2-双(双(3，5-二正烷基苯基)膦基甲基)环丁烷选自由反式-1，2-双(双(3，5-甲基苯基)膦基甲基)环丁烷、反式-1，2-双(双(3，5-二乙基苯基)膦基甲基)环丁烷和反式-1，2-双(双(3，5-二正丙基苯基)膦基甲基)环丁烷组成的组，其中所述铑络合物包含铑和配体，所述配体选自由氢、羰基、三烷基膦或三芳基膦、二膦、环戊二烯基、2，4-链烷双酸根和它们的混合物组成的组。
2.权利要求1的方法，其中所述催化剂体系包含所述铑络合物和反式-1，2-双(双(3，5-二甲基苯基)膦基甲基)环丁烷。
3.权利要求1的方法，其中所述催化剂体系包含所述铑络合物和反式-1，2-双(双(3，5-二乙基苯基)膦基甲基)环丁烷。
4.权利要求1的方法，其中所述溶剂选自由C5-C20脂族烃、C6-C12芳族烃、醚、醇和它们的混合物组成的组。
5.权利要求1的方法，其中所述溶剂选自由甲苯、环己烷、甲基叔丁基醚和它们的混合物组成的组。
6.权利要求1的方法，其中所述反应在45℃-85℃范围内的温度下和30-400psig范围内的压力下进行。
7.权利要求1的方法，其中所述催化剂体系还包含单膦化合物。
8.权利要求7的方法，其中所述单膦化合物是三苯基膦。
9.权利要求1的方法，还包括在加氢催化剂的存在下加氢所述4-羟基丁醛以生成1，4-丁二醇。
10.权利要求9的方法，其中所述加氢催化剂是镍催化剂。
11.包含铑络合物和反式-1，2-双(双(3，5-二正烷基苯基)膦基甲基)环丁烷的催化剂，所述反式-1，2-双(双(3，5-二正烷基苯基)膦基甲基)环丁烷选自由反式-1，2-双(双(3，5-二甲基苯基)膦基甲基)环丁烷、反式-1，2-双(双(3，5-二乙基苯基)膦基甲基)环丁烷和反式-1，2-双(双(3，5-二正丙基苯基)膦基甲基)环丁烷组成的组，其中所述铑络合物包含铑和配体，所述配体选自由氢、羰基、三烷基膦或三芳基膦、二膦、环戊二烯基、2，4-链烷双酸根和它们的混合物组成的组。
12.权利要求11的催化剂，其中所述催化剂体系包含铑络合物和反式-1，2-双(双(3，5-二甲基苯基)膦基甲基)环丁烷。
13.权利要求11的催化剂，其中所述催化剂体系包含铑络合物和反式-1，2-双(双(3，5-二乙基苯基)膦基甲基)环丁烷。
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| CN1816513A (zh) * | 2003-07-03 | 2006-08-09 | 卢西特国际英国有限公司 | 烯属不饱和化合物的加氢甲酰基化方法 |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2010523558A (ja) | 2010-07-15 |
| KR20090126270A (ko) | 2009-12-08 |
| KR101504517B1 (ko) | 2015-03-23 |
| WO2008121194A8 (en) | 2010-04-29 |
| ES2423017T3 (es) | 2013-09-17 |
| EP2131957A1 (en) | 2009-12-16 |
| JP5296048B2 (ja) | 2013-09-25 |
| WO2008121194A1 (en) | 2008-10-09 |
| TWI443083B (zh) | 2014-07-01 |
| US7279606B1 (en) | 2007-10-09 |
| TW200840808A (en) | 2008-10-16 |
| EP2131957B1 (en) | 2013-06-12 |
| CN101652179A (zh) | 2010-02-17 |
| US7294602B1 (en) | 2007-11-13 |
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