CN108525704A - 用于烯烃氢甲酰化反应的催化剂及其制备方法和应用 - Google Patents
用于烯烃氢甲酰化反应的催化剂及其制备方法和应用 Download PDFInfo
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- CN108525704A CN108525704A CN201810380774.XA CN201810380774A CN108525704A CN 108525704 A CN108525704 A CN 108525704A CN 201810380774 A CN201810380774 A CN 201810380774A CN 108525704 A CN108525704 A CN 108525704A
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- hydroformylation
- olefin
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- bidentate
- phosphoramide
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- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 36
- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 31
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003446 ligand Substances 0.000 claims abstract description 58
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 11
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- 238000006243 chemical reaction Methods 0.000 claims description 41
- 239000010948 rhodium Substances 0.000 claims description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 16
- KTDISHMAKPRCQI-UHFFFAOYSA-N P(=O)(N)(N)N.P Chemical compound P(=O)(N)(N)N.P KTDISHMAKPRCQI-UHFFFAOYSA-N 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 15
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 14
- 229910052703 rhodium Inorganic materials 0.000 claims description 14
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 13
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- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical compound NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
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- 239000002184 metal Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
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- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical group [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 claims description 4
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- 239000008096 xylene Substances 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 2
- -1 alkene Hydrocarbon Chemical class 0.000 claims 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 9
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- 150000008300 phosphoramidites Chemical class 0.000 abstract description 5
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- 150000001299 aldehydes Chemical class 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical class CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical class CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 0 *P(*)N1C=C(Cc(c2c3cccc2)c[n]3P(*)*)C2=CC=CCC12 Chemical compound *P(*)N1C=C(Cc(c2c3cccc2)c[n]3P(*)*)C2=CC=CCC12 0.000 description 3
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- 238000006555 catalytic reaction Methods 0.000 description 3
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- 150000002475 indoles Chemical class 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 3
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- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
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- 150000001412 amines Chemical class 0.000 description 2
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- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
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- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 2
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- YKFRUJSEPGHZFJ-UHFFFAOYSA-N N-trimethylsilylimidazole Chemical compound C[Si](C)(C)N1C=CN=C1 YKFRUJSEPGHZFJ-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- JLENGJWAMLTKIB-UHFFFAOYSA-N [Cl].[O].[P].C1=CC=CC=C1 Chemical compound [Cl].[O].[P].C1=CC=CC=C1 JLENGJWAMLTKIB-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
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- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002027 dichloromethane extract Substances 0.000 description 1
- XSQNOFMFKVYSNL-UHFFFAOYSA-N ethene;toluene Chemical group C=C.CC1=CC=CC=C1 XSQNOFMFKVYSNL-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- RYPKRALMXUUNKS-UHFFFAOYSA-N hex-2-ene Chemical class CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- VSPPONOIKZXUBJ-UHFFFAOYSA-N n,n-diethylethanamine;oxolane Chemical compound C1CCOC1.CCN(CC)CC VSPPONOIKZXUBJ-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
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- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229940117958 vinyl acetate Drugs 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
- B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
- B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
- B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
- B01J31/2457—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings, e.g. Xantphos
-
- 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
- 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
-
- 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
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0073—Rhodium compounds
- C07F15/008—Rhodium compounds without a metal-carbon linkage
-
- 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
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0244—Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及一类多齿亚磷酰胺膦配体的制备方法和应用,是涉及一类含氮杂环骨架的多齿亚磷酰胺膦配体用作烯烃氢甲酰化反应的催化剂的制备和应用方法。本发明提供的用于烯烃氢甲酰化反应的催化剂及其制备方法和应用,提供了具有含氮杂环2‑(3‑吲哚基)甲烷和1,1,2,2‑四(3‑吲哚基)乙烷作为骨架的双齿或多齿亚磷酰胺类膦配体的合成,该配体修饰的催化剂用于含烯烃结构的氢甲酰化反应时,与现有催化剂体系相比,该催化剂体系在较低温度和较低压力下具有较好的活性,该催化剂在制备和使用过程中具有很好的稳定性,制备方法简单,具有实用价值。
Description
技术领域
本发明涉及一类多齿亚磷酰胺膦配体的制备方法和应用,具体说,是涉及一类含氮杂环骨架的多齿亚磷酰胺膦配体用作烯烃氢甲酰化反应的催化剂的制备和应用方法,属于有机化学技术领域。
背景技术
氢甲酰化反应是指烯烃与合成气(H2+CO)在催化剂的作用下生成多一个碳的支链醛和直链醛的反应。自Otto Roelen教授1938年发现该反应以来,氢甲酰化反应已成为当今工业应用中最重要的化学反应之一。
氢甲酰化反应中膦配体的合成一直是一个研究热点,膦配体按照与P相连原子不同,可以分为全为P-C键的膦配体,含有P-O键的亚磷酸酯类膦配体,含有P-N键的亚磷酰胺类膦配体,亚磷酰胺类膦配体由于其合成简便,结构稳定,效果优越等特点,在氢甲酰化反应中倍受青睐。
亚磷酰胺类膦配体虽然种类繁多,但多是以含氮杂环如吡咯、吲哚等作为取代基,以苯环、联苯等作为骨架,少见以含氮杂环直接作为骨架合成的膦配体。同时,配体的稳定性是评估膦配体工业应用的重要考量因素。迄今为止,文献报道与氢甲酰化相关的配体多达数百种,但是工业中得以应用发展的却很少。膦配体的不稳定性限制了其工业应用的价值,因此探索具有好的稳定性和高的催化活性的膦配体是研究中的一个重点。
发明内容
本发明的目的是提供一类具有含氮骨架的亚磷酰胺类膦配体的制备方法,及其在氢甲酰化中的应用,为氢甲酰化反应提供了一类稳定的具有高活性的催化剂的制备。
本发明的技术方案:
用于烯烃氢甲酰化反应的催化剂,由铑络合物和双齿或多齿亚膦酰胺膦配体制备所得,双齿或多齿亚膦酰胺膦配体与铑络合物中金属铑的摩尔比为1-100:1;反应温度为:0-120℃,反应时间0.1-24h;
所述双齿或多齿亚膦酰胺膦配体的通式为:
其中,其中,n=1,2,3,4,R1为含氮或不含氮的芳香环或含有联苯或联萘结构的基团,如苯基、N-咪唑基、N-吲哚基、N-咔唑基或中的一种。
优选的,金属铑与双齿亚膦酰胺膦配体的摩尔比为2-30:1,反应温度30-100℃,反应时间0.5-10h。
进一步,上述铑化合物选自Rh(acac)(CO)2、RhCl3、[Rh(cod)Cl]2、[Rh(CO)2Cl]2、Rh(acac)(C2H4)或[Rh(C2H4)2Cl]2中的至少一种,其中,acac为乙酰丙酮,cod代表1,4-环辛二烯。
优选的,
所述双齿或多齿亚膦酰胺配体为双膦配体,双膦配体或之结构相对应的四膦配体为:
更优选的,所述双齿亚膦酰胺或亚膦酸酯膦配体为:
用于烯烃氢甲酰化反应的催化剂的制备方法,包括以下过程:
在惰性气体保护下,将铑络合物和双齿或多齿亚膦酰胺膦配体于溶剂中搅拌混匀得到铑-双齿或铑-多齿亚膦酰胺膦配体催化剂;金属铑在溶剂中的浓度为5×10-4-6×10- 3mol/L;
所述溶剂为苯、甲苯、二甲苯、三甲苯、氯仿、二氯甲烷、四氢呋喃、二甲基亚砜或乙腈中的至少一种。
该催化剂的制备过程可用下面反应式表示:
进一步,上述方法中,所述双齿或多齿亚膦酰胺膦配体的制备方法,包括以下过程:
将磷氯与2-(3-吲哚基)甲烷或1,1,2,2-四(3-吲哚基)乙烷化合物反应得到,该过程可用下面的反应式表示:
用于烯烃氢甲酰化反应的催化剂的应用于烯烃氢甲酰化反应:氢气、一氧化碳和C2-C18烯烃在溶剂中,于30-100℃反应温度下,总气体压力为0.5-5.0Mpa下在上述催化剂的作用下反应生成含有醛基的化合物,其中,C2-C18烯烃与催化剂的摩尔比例为100-10000。
所用C2-C18烯烃中,C4-C18烯烃可以为链状端烯烃或中间烯烃,如1-丁烯、1-己烯、1-辛烯、2-丁烯、2-己烯、2-辛烯等。
该催化剂除用于简单烯烃氢甲酰化反应,还可用于其他含官能团或取代基的烯烃化合物的氢甲酰化反应,如丙烯酸酯、醋酸乙烯酯、环戊二烯、降冰片二烯、苯乙烯、甲基苯乙烯等。
上述氢甲酰化反应所述溶剂为苯、甲苯、二甲苯、三甲苯、氯仿、二氯甲烷、四氢呋喃、二甲基亚砜或乙腈中的至少一种。
本发明提供的用于烯烃氢甲酰化反应的催化剂及其制备方法和应用,提供了具有含氮杂环2-(3-吲哚基)甲烷和1,1,2,2-四(3-吲哚基)乙烷作为骨架的双齿或多齿亚磷酰胺类膦配体的合成,该配体修饰的催化剂用于含烯烃结构的氢甲酰化反应时,与现有催化剂体系相比,该催化剂体系在较低温度和较低压力下具有较好的活性,该催化剂在制备和使用过程中具有很好的稳定性,制备方法简单,具有实用价值。
具体实施方式
通过下述实施例有助于进一步理解本发明,但不限制发明内容。
实施例1
2-(3-吲哚基)甲烷骨架的合成:
将吲哚(1.17g,10mmol),CTAB(50%mol)及草酸(50%mol)置于25ml单口圆底烧瓶中,加入5毫升去离子水。充分搅拌5分钟后,滴加甲醛水溶液(0.38g溶液,5mmol甲醛)。室温反应3小时,停止反应。用15ml乙酸乙酯分三次萃取反应液,收集有机相后用无水Na2SO4干燥5小时。减压除去溶剂,用甲醇与水的混合溶液重结晶(甲醇/H2O=10/1),得白色固体,产率85%。
1H NMR(400MHz,DMSO-d6):δ=10.72(s,N-H),7.51(d,J=7.8Hz,2H),7.31(d,J=8.1Hz,2H),7.12(s,2H),7.02(t,J=7.6Hz,2H),6.91(t,J=7.9Hz,2H),4.12(s,2H)。
实施例2
1,1,2,2-四(3-吲哚基)乙烷的合成:
将吲哚(1.17g,10mmol)及草酸(50%mol)置于25ml单口圆底烧瓶中,加入5毫升乙醇,并充分搅拌5分钟。滴加乙二醛水溶液(0.37g水溶液,2.5mmol乙二醛),室温反应24小时,反应过程中有黄褐色固体生成。停止反应后,减压除去乙醇溶剂,并加入10ml去离子水,用15ml乙酸乙酯分三次萃取反应物,然后经无水Na2SO4干燥5小时。减压除去乙酸乙酯,用DMF与水的混合溶液重结晶,得淡黄色固体,产率75%。
1H NMR(400MHz,DMSO-d6):δ=9.53(s,N-H),7.50(d,J=7.9Hz,4H),7.06(d,J=8.1Hz,4H),6.98(s,4H),6.79(t,J=7.5Hz,4H),6.70(t,J=7.4Hz,4H),5.66(s,2H)。
实施例3
双齿亚膦酰胺膦配体的合成:
在N2或者Ar气体氛围下,向一50ml三口瓶中分别加入无水四氢呋喃(10ml)和二苯基磷氯(2.2mmol,0.49g),0℃条件下滴加二(3-吲哚基)甲烷(1mmol,0.246g)和三乙胺(1ml)的无水四氢呋喃(10ml)溶液,缓慢滴加完毕后,温度升至50℃并搅拌过夜。停止反应并静止30分钟,在氮气保护下除去三乙胺盐酸盐,减压除去溶剂,剩余物经柱色谱分离得配体(硅胶:300-400目,洗脱剂:正己烷/二氯甲烷/三乙胺=10/1/0.01),白色固体,产率45%。
1H NMR(400MHz,CDCl3):δ=7.78(dd,J=8.2,0.8Hz,2H),7.45(d,J=7.8Hz,2H),7.40–7.27(m,20H),7.20(dd,J=8.2,7.2Hz,2H),7.08(t,J=7.5Hz,2H),6.82(s,2H),4.10(s,2H)。
实施例4
多齿亚膦酰胺膦配体的合成:
在N2或者Ar气体氛围下,向一50ml三口瓶中分别加入无水四氢呋喃(10ml)和二苯基磷氯(4.4mmol,0.98g),0℃条件下滴加1,1,2,2-四(3-吲哚基)乙烷(1mmol,0.5g)和三乙胺(2ml)的无水四氢呋喃(10ml)溶液,缓慢滴加完毕后,温度升至50℃并搅拌过夜。停止反应并静止30分钟,在氮气保护下除去三乙胺盐酸盐,减压除去溶剂,剩余物经柱色谱分离得配体(硅胶:300-400目,洗脱剂:正己烷/二氯甲烷/三乙胺=10/1/0.01),得白色固体,产率40%。
1H NMR(400MHz,CDCl3):δ=7.80(d,J=7.5Hz,4H),7.38–6.82(m,52H),6.61(s,4H),5.31(d,J=16.0Hz,2H)。
实施例5
双齿亚膦酰胺膦配体的合成:
连苯氧磷氯由三氯化磷和联苯酚合成:在N2或者Ar气体氛围下保护下,向50ml三颈瓶中加入联苯酚(12mmol,2.23g)重蒸的三氯化磷(30ml),用NaOH水溶液作为尾气吸收,在回流状态下反应1h后停止反应,通过减压蒸馏(0.1mmHg)除去多余的三氯化磷,再用15ml甲苯洗涤三次,并通过减压蒸馏除去,得到红色油状液体,直接用于下一步反应。
在N2或者Ar气体氛围下,在100ml的三颈瓶中,将新制的在保护下转移进来,并加入25ml重蒸的四氢呋喃,N2保护下,在-20℃下,在30分钟内滴加和三乙胺(5ml)的四氢呋喃(20ml)溶液。滴加结束后,恢复室温下反应12小时后停止反应。静置20分钟,然后N2气氛下针滤以除去三乙胺盐酸盐,减压除去溶剂四氢呋喃。得到淡黄色油状物。随后用处理后的二氯甲烷萃取。减压除去二氯甲烷,得到白色固体产物,产率70%。
1H NMR(400MHz,CDCl3)δ7.83–6.50(m,14H),3.80(s,1H)。
实施例6—实施例18
用于烯烃氢甲酰化反应的催化剂的应用:
在60ml高压反应釜中,依次加入Rh(acac)(CO)2(acac=乙酰丙酮)1.6mg(0.00637mmol),底物1-辛烯1ml(0.00637mol),溶剂甲苯(3ml),膦配体(19.5mg,0.0318mmol);随后充入合成气置换三次,再次冲入合成气至20bar;迅速升温至所100℃并开始搅拌,计时;反应2h后结束,将高压反应釜置于冰水中快速冷却,取出反应液;氢甲酰化产物用Agilent GC-6890N气相色谱仪定量分析,毛细管柱采用SE-30,氢火焰检测器。
实施例6-实施例11的反应过程如下,配体P/Rh比如表1:
表1配体P/Rh比的筛选(实施例6-实施例10)a
a反应条件:Rh(acac)(CO)2的浓度为1.5mmol/L,底物与催化剂的比例为1000,1-辛烯的体积为1mL,甲苯3mL,100℃,反应压力为2MPa,反应时间为120min。b产物中生成的醛所占摩尔百分比例;c产物中生成的辛烷所占摩尔百分比例;d产物中生成的2-辛烯所占摩尔百分比例;e.产物中直链醛与支链醛的摩尔比。
实施例11-实施例15的反应过程如下,反应为温度的筛选如表2:
表2反应为温度的筛选(实施例11-实施例15)a
a反应条件:Rh(acac)(CO)2的浓度为1.5mmol/L,底物与催化剂的比例为1000,1-辛烯的体积为1mL,甲苯3mL,P的浓度与Rh(acac)(CO)2浓度比为10,反应压力为2MPa,反应时间为120min。b产物中生成的醛所占摩尔百分比例;c产物中生成的辛烷所占摩尔百分比例;d产物中生成的2-辛烯所占摩尔百分比例;e.产物中直链醛与支链醛的摩尔比;f反应时间为12h。
实施例16-实施例18的反应过程如下,反应为压力的筛选如表3:
表3反应为压力的筛选(实施例16-实施例18)a
a反应条件:Rh(acac)(CO)2的浓度为1.5mmol/L,底物与催化剂的比例为1000,1-辛烯的体积为1mL,甲苯3mL,P的浓度与Rh(acac)(CO)2浓度比为10,反应温度60℃,反应压力为2MPa,反应时间为120min。
b产物中生成的醛所占摩尔百分比例;c产物中生成的辛烷所占摩尔百分比例;d产物中生成的2-辛烯所占摩尔百分比例;e.产物中直链醛与支链醛的摩尔比。
实施例19
多齿亚膦酰胺配体的Rh络合物催化1-辛烯的氢甲酰化:
在60ml高压反应釜中,依次加入Rh(acac)(CO)2(acac=乙酰丙酮)1.6mg(0.00637mmol),底物1-辛烯1ml(0.00637mol),溶剂甲苯(3ml),多齿亚膦酰胺配体(29.2mg,0.0238mmol)。随后充入合成气置换三次,再次冲入合成气至20bar。迅速升温至所60℃并开始搅拌,计时。反应2h后结束,将高压反应釜置于冰水中快速冷却,取出反应液。氢甲酰化产物用Agilent GC-6890N气相色谱仪定量分析。正异比为2.5,转化率97.7%,醛的选择性为94.1%。
实施例20
双齿亚膦酸酯配体的Rh络合物催化1-辛烯的氢甲酰化:
在60ml高压反应釜中,依次加入Rh(acac)(CO)2(acac=乙酰丙酮)1.6mg(0.00637mmol),底物1-辛烯1ml(0.0637mol),溶剂甲苯(3ml),双齿亚膦酸酯配体(10.73mg,0.0159mmol)。随后充入合成气置换三次,再次冲入合成气至20bar。迅速升温至所60℃并开始搅拌,计时。反应2h后结束,将高压反应釜置于冰水中快速冷却,取出反应液。氢甲酰化产物用Agilent GC-6890N气相色谱仪定量分析。正异比为3.2,转化率为98.5%,醛的选择性为95.3%。
Claims (9)
1.一种用于烯烃氢甲酰化反应的催化剂,其特征在于:由铑络合物和含吲哚环的双齿或多齿亚膦酰胺配体制备所得,双齿或多齿亚膦酰胺配体与铑络合物中金属铑的摩尔比为1-100:1;
所述双齿或多齿亚膦酰胺膦配体的通式为:
其中,n=1,2,3,4;R1为含氮或不含氮的芳香环或含有联苯或联萘结构的基团:
2.根据权利要求1所述的用于烯烃氢甲酰化反应的催化剂,其特征在于:所述的铑络合物中的金属铑与双齿亚膦酰胺膦配体的摩尔比为1:1-30。
3.根据权利要求1所述的用于烯烃氢甲酰化反应的催化剂,其特征在于:所述的铑化合物为Rh(acac)(CO)2、RhCl3、[Rh(cod)Cl]2、[Rh(CO)2Cl]2、Rh(acac)(C2H4)或[Rh(C2H4)2Cl]2中的至少一种,其中,acac为乙酰丙酮,cod代表1,4-环辛二烯。
4.根据权利要求1所述的用于烯烃氢甲酰化反应的催化剂,其特征在于:所述双齿或多齿亚膦酰胺配体为双膦配体,双膦配体或之结构相对应的四膦配体为:
5.根据权利要求1所述的用于烯烃氢甲酰化反应的催化剂,其特征在于:所述双齿或多齿亚膦酰胺膦配体为:
6.根据权利要求1到5任一项所述的用于烯烃氢甲酰化反应的催化剂的制备方法,其特征在于,包括以下过程:
在惰性气体保护下,将铑络合物和双齿或多齿亚膦酰胺膦配体于溶剂中搅拌混匀得到铑-双齿亚膦酰胺配体或铑-多齿亚膦酰胺配体催化剂;金属铑在溶剂中的浓度为5×10- 4mol/L-6×10-3mol/L;
所述溶剂为苯、甲苯、二甲苯、三甲苯、氯仿、二氯甲烷、四氢呋喃、二甲基亚砜或乙腈中的至少一种。
7.双齿或多齿亚膦酰胺膦配体的制备方法,其特征在于,上述的双齿或多齿亚膦酰胺膦配体的制备过程:
将磷氯与2-(3-吲哚基)甲烷或1,1,2,2-四(3-吲哚基)乙烷化合物反应得到,反应式为:
8.根据权利要求1所述的用于烯烃氢甲酰化反应的催化剂的应用,其特征在于,用于烯烃氢甲酰化反应:氢气、一氧化碳和C2-C18烯烃在溶剂中,于30-120℃反应温度下,总气体压力为0.5-5.0Mpa下在上述催化剂的作用下反应生成含有醛基的化合物,其中,C2-C18烯烃与催化剂的摩尔比例为100-10000。
9.根据权利要求8所述的用于烯烃氢甲酰化反应的催化剂的应用,其特征在于,所用C2-C18烯烃中,C4-C18烯烃为链状端烯烃或中间烯烃或环状烯烃。
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