CN1543469A - 新的亚磷酸酯化合物和其金属配合物 - Google Patents
新的亚磷酸酯化合物和其金属配合物 Download PDFInfo
- Publication number
- CN1543469A CN1543469A CNA028160525A CN02816052A CN1543469A CN 1543469 A CN1543469 A CN 1543469A CN A028160525 A CNA028160525 A CN A028160525A CN 02816052 A CN02816052 A CN 02816052A CN 1543469 A CN1543469 A CN 1543469A
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- China
- Prior art keywords
- aliphatic series
- phosphorous acid
- acid ester
- aromatics
- requires
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 34
- 239000002184 metal Substances 0.000 title claims abstract description 34
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 title claims description 6
- 239000003446 ligand Substances 0.000 claims abstract description 38
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 36
- 150000001336 alkenes Chemical class 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- -1 phosphorous acid ester Chemical class 0.000 claims description 75
- 125000001931 aliphatic group Chemical group 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 28
- 239000010948 rhodium Substances 0.000 claims description 20
- 229910052703 rhodium Inorganic materials 0.000 claims description 18
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 125000001072 heteroaryl group Chemical group 0.000 claims description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 9
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000002723 alicyclic group Chemical group 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 125000000623 heterocyclic group Chemical group 0.000 claims description 7
- 238000007172 homogeneous catalysis Methods 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 4
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 125000001475 halogen functional group Chemical group 0.000 claims 3
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 3
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 abstract 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 24
- 239000003054 catalyst Substances 0.000 description 16
- 239000007789 gas Substances 0.000 description 15
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 12
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 150000003254 radicals Chemical group 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 150000001299 aldehydes Chemical class 0.000 description 6
- 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 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 5
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 4
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 3
- UPHOPMSGKZNELG-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=C(O)C=CC2=C1 UPHOPMSGKZNELG-UHFFFAOYSA-N 0.000 description 3
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- 238000004679 31P NMR spectroscopy Methods 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 150000001869 cobalt compounds Chemical class 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
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- 229910052759 nickel Inorganic materials 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
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- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 2
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- KYLUAQBYONVMCP-UHFFFAOYSA-N (2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P KYLUAQBYONVMCP-UHFFFAOYSA-N 0.000 description 1
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- BZJTUOGZUKFLQT-UHFFFAOYSA-N 1,3,5,7-tetramethylcyclooctane Chemical group CC1CC(C)CC(C)CC(C)C1 BZJTUOGZUKFLQT-UHFFFAOYSA-N 0.000 description 1
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
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- 125000001624 naphthyl group Chemical group 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
- MXRGQMSYIGWYQS-UHFFFAOYSA-N nonanoic acid;rhodium Chemical compound [Rh].CCCCCCCCC(O)=O MXRGQMSYIGWYQS-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pent-2-ene Chemical group CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- PDEDQSAFHNADLV-UHFFFAOYSA-M potassium;disodium;dinitrate;nitrite Chemical compound [Na+].[Na+].[K+].[O-]N=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PDEDQSAFHNADLV-UHFFFAOYSA-M 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- IFXORIIYQORRMJ-UHFFFAOYSA-N tribenzylphosphane Chemical compound C=1C=CC=CC=1CP(CC=1C=CC=CC=1)CC1=CC=CC=C1 IFXORIIYQORRMJ-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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Abstract
本发明涉及具有下式I或II的亚磷酸酯和它们的金属配合物,它们的制备和所述亚磷酸酯作为催化反应中的配位体的应用,特别是在烯烃的加氢甲酰基化方法中。
Description
本发明涉及亚磷酸酯和其金属配合物,制备和在催化反应中作为配位体的亚磷酸酯的应用。
在催化剂存在的条件下烯烃化合物,一氧化碳和氢形成具有多一个碳的醛的反应称作加氢甲酰基化(羰基合成)。作为这些反应中的催化剂,经常利用元素周期表的第8-10族中的过渡金属的化合物,特别是铑和钴化合物。与钴化合物催化相比,使用铑化合物的加氢甲酰基化通常提供了更高选择性的优势,因此通常更经济。就铑催化的加氢甲酰基化而言,通常使用包含铑和优选三价磷化合物作为配位体的配合物。已知的配位体是,例如,来自于膦类,亚磷酸酯类和亚膦酸酯类的化合物。烯烃加氢甲酰基化的概况可以参见B.CORNILS,W.A.HERRMANN,“Applied Homogeneous Catalysis with OrganometallicCompounds(用有机金属化合物的应用均相催化)”,1&2卷,VCH,Weinheim,纽约,1996。
每一种催化剂系统(铑或钴)具有自身的特定优点。取决于初始原料和目标产品,使用不同的催化剂系统。如果使用铑和三苯基膦,则α-烯烃可以在相对低的压力下加氢甲酰基化。通常使用过量的三苯基膦作为含磷配位体,其中高的配位体/铑比率对于增加反应的选择性以产生商业上理想的正醛产品是必须的。
US-A-4,694,109和US-A-4,879,416涉及二膦配位体和其在较低的合成气体压力下在烯烃的加氢甲酰基化中的应用。特别是在丙烯的加氢甲酰基化中,使用这种类型的配位体取得了高活性和高正/异选择性。
WO-A-95/30680描述了二齿膦配位体和其在催化中的应用,特别是在加氢甲酰基化反应中。
例如,在US-A-4,169,861,US-A-4,201,714和US-A-4,193,943中揭示了作为加氢甲酰基化配位体的二茂铁桥联的二膦。
二齿膦配位体的缺点是它们相对复杂的制备。因此在工业方法中使用这种系统通常在经济上是没有前途的。
铑-一亚磷酸酯配合物对于具有内部双键的支链烯烃的加氢甲酰基化是合适的催化剂,但是对于末端加氢甲酰基化的化合物的选择性是低的。EP-A-0155508公开了在立体位阻烯烃,例如异丁烯的铑催化加氢甲酰化中使用二亚芳基取代的一亚磷酸酯。
铑-二亚磷酸酯配合物催化具有末端和内部双键的线性烯烃的加氢甲酰基化,主要产生末端加氢甲酰基化产品,与此相反具有内部双键的支链烯烃仅在小程度上反应。在过渡金属中心的配位中,这些亚磷酸酯产生了具有增加活性的催化剂,但是这些催化剂系统的使用寿命不令人满意,特别是因为亚磷酸酯配位体的水解敏感性。正如在EP-A-0 214 622或EP-A-0 472 071中所描述的,使用取代双芳基二醇作为亚磷酸酯配位体的初始原料,已经可获得极大的改善。
根据文献,这些配位体的铑配合物是α-烯烃的极其活性的加氢甲酰基化催化剂。US-A-4,668,651,US-A-4,748,261和US-A-4,885,401中描述聚亚磷酸酯配位体,通过它α-烯烃还有二丁烯可以被高选择性地转化成末端加氢甲酰基化产品。在US-A-5,312,996中,这种类型的二齿配位体也用于丁二烯的加氢甲酰基化。
尽管提到的二亚磷酸酯对于铑加氢甲酰基化催化剂是好的配合物配位体,但是开发新型的易于制备的亚磷酸酯进一步改进例如在加氢甲酰基化中的有效性是理想的。
已经惊人的发现具有以下通式结构I或II的新的亚磷酸酯是合适的配合物配位体,
其中R1,R2,R3和R4每一个独立选自单价取代或未取代的脂族的、脂环族的芳族的、杂芳族的、混合脂族-脂环族的、混合脂族-芳族的、杂环的、混合脂族-杂环的具有1-50个碳原子的烃基,H,F,Cl,Br,I,-CF3,-CH2(CF2)jCF3,其中j=0-9,-OR9,-COR9,-CO2R9,-CO2M,-SR9,-SO2R9,-SOR9,-SO3R9,-SO3M,-SO2NR9R10,-NR9R10,-N=CR9R10,其中R9和R10各自独立选自H,单价取代或未取代的脂族的和芳族的具有1-25个碳原子的烃基,并且M是碱金属离子,形式上半碱土金属离子,铵离子或鏻离子,
或相邻的基团R1到R4一起形成稠合取代的或未取代的芳族的、杂芳族的、脂族的、混合芳族-脂族的或混合杂芳族-脂族的环系统;
Q是k价的取代或未取代的脂族的、脂环族的、混合脂族-脂环族的、杂环的、混合脂族-杂环的、芳族的、混合脂族-芳族的具有1-50个碳原子的烃基,其中Q的脂族部分可以包含氧,硫和/或氮,
k是至少2并且在与Q相连的各个结构单元中的R1,R2,R3和R4可以彼此不同。如果在与Q相连的各个结构单元中的基团R1到R4彼此不同,则亚磷酸酯是不对称的。
本发明也提供了具有元素周期表第4,5,6,7,8,9或10族金属的亚磷酸酯配位体的配合物和其制备。
本发明进一步提供了亚磷酸酯和亚磷酸酯-金属配合物在催化中的应用,优选在均相催化中,特别是在烯烃的加氢甲酰基化中。
本发明的另一个方面是烯烃的加氢甲酰基化的方法和制备亚磷酸酯配位体的方法。
在优选的具有式I或II的亚磷酸酯中,至少两个相邻的基团R1到R4一起形成稠合的芳族的、杂芳族的、脂族的、混合芳族-脂族的或混合杂芳族-脂族的环系统,其可以是未取代的或被选自下列的至少一个基团取代:脂族的、脂环族的、芳族的、杂芳族的、混合脂族-脂环族的、混合脂族-芳族的、杂环的、混合脂族-杂环的具有1-50个碳原子的烃基,F,Cl,Br,I,-CF3,-CH2(CF2)jCF3,其中j=0-9,-OR9,-COR9,-CO2R9,-CO2M,-SR9,-SO2R9,-SOR9,-SO3R9,-SO3M,-SO2NR9R10,-NR9R10或-N=CR9R10,其中R9,R10和M如上所定义。
在式I或II的亚磷酸酯中,Q优选是二价到四价的基团。例如,Q可以具有在下式III中显示的通式结构,
其中R11,R12,R13,R14,R15,R16,R17和R18如权利要求1或2中所定义的R1到R4,W是二价基团CR19R20,其中R19和R20如R9和R10所定义,m=0-1并且位置a和b代表连接点。相邻的基团R11到R18可以以与式(I)或(II)中的R1到R4相似的方式一起形成稠合取代或未取代的芳族的、杂芳族的、脂族的、混合芳族-脂族的或混合杂芳族-脂族的环系统。该环系统优选被选自下列的至少一个基团取代:脂族的、脂环族的、芳族的、杂芳族的、混合脂族-脂环族的、混合脂族-芳族的、杂环的、混合脂族-杂环的具有1-50个碳原子的烃基,F,Cl,Br,I,-CF3,-CH2(CF2)jCF3,其中j=0-9,-OR9,-COR9,-CO2R9,-CO2M,-SR9,-SO2R9,-SOR9,-SO3R9,-SO3M,-SO2NR9R10,-NR9R10或-N=CR9R10,其中R9,R10和M如上所定义。
其它的Q的例子是苯基,萘基,二芳基,二苯基醚的基团或具有与下式IV相对应的结构的杯[正]芳烃基团:
其中R21,R22和R23各自独立地选自取代或未取代的具有1-25个碳原子的脂族的和芳族的烃基,H,F,Cl,Br,I,-CF3,-CH2(CF2)jCF3,其中j=0-9,-OR24,-COR24,-CO2R24,-CO2M,-SR24,-SO2R24,-SOR24,-SO3R24,-SO3M,-SO2NR24R25,-NR24R25和-N=CR24R25,其中R24和R25如R9和R10所定义并且M是碱金属离子,形式上半碱土金属离子,铵离子或鏻离子,或相邻的基团R21到R23一起形成稠合取代的或未取代的芳族的、杂芳族的,脂族的、混合芳族-脂族的或混合杂芳族-脂族的环系统;Y是二价基团CR24R25或CR24R25-O-CR24R25,n=3-6并且位置a代表连接点或表示OR24,其中R24和R25如上所定义。
代表性的具有式I或II的亚磷酸酯配位体是:
例(I)到(M)是不对称的亚磷酸酯。
根据本发明使用的亚磷酸酯可以通过磷-卤化物与醇,羧酸和/或α-羟基芳基羧酸的一系列反应制备,其中磷上的卤原子被氧基团替换。制备本发明的亚磷酸酯的许多可能性中的一个是下面的二亚磷酸酯的合成路线:
在第一步中,在碱存在下,α-羟基芳基羧酸(1)与三卤化磷PX3,例如PCl3,PBr3和PI3,优选三氯化磷PCl3,反应形成卤代二氧杂磷杂环己酮(Halogendioxaphosphorinon)(2),碱优选以当量量或催化量使用。
在第二反应步骤中,在碱存在下,卤代二氧杂磷杂环己酮(2)与二醇(HO-Q-OH)或二羧酸(HOOC-Q-COOH)反应产生理想的亚磷酸酯(I)或(II),碱优选以当量量或催化量使用。
基团R1到R4和Q如上所定义。
在不对称的二亚磷酸酯的合成中,两个不同取代的氯代二氧杂磷杂环酮(2a)和(2b),其中在(2a)和(2b)中至少一个基团R1到R4具有不同的含义,它们在第一反应步骤中制备和之后这些,在第二反应步骤中,在碱存在的条件下它们顺序与二醇或二羧酸反应,碱优选以当量量或催化的量使用。
因为使用的二醇或二羧酸和其下游产品通常是固体,所以反应通常在溶剂中进行。使用的溶剂是非质子溶剂,其既不与二醇也不与二羧酸也不与磷化合物反应。合适的溶剂的例子是四氢呋喃,醚,例如乙醚或MTBE(甲基叔丁基醚)和芳族烃,例如甲苯。
磷-卤化物和醇的反应形成卤化氢,其被添加的碱结合。可用于此目的的碱的例子是叔胺,例如三乙基胺,吡啶或N-甲基吡咯烷二酮。部分地在反应前把醇转化成金属醇盐也是有用的,例如通过与氢化钠或丁基锂反应。
亚磷酸酯是与元素周期表第4,5,6,7,8,9或10族金属配合的合适的配位体。配合物可以包含一个或多个亚磷酸酯配位体和任选地,进一步的配位体并且作为催化剂是适合的,优选在均相催化中。适合的金属的例子是铑,钴,铱,镍,钯,铂,铁,钌,锇,铬,钼和钨。特别就第8,9或10族的金属而言,产生的配合物可以用作加氢甲酰基化,羰基化,氢化和氢氰化反应的催化剂,特别优选铑,钴,镍,铂和钌。例如,特别是作为催化剂金属的铑的应用中在加氢甲酰基化反应中产生了高的催化活性。催化剂金属以盐或配合物的形式使用,就铑而言,例如,羰基铑,硝酸铑,三氯化铑,Rh(CO)2(acac)(acac二乙酰基丙酮酸根),乙酸铑,辛酸铑或壬酸铑。
均相催化的活性催化剂种类由本发明的亚磷酸酯配位体和催化剂金属在反应条件下形成,例如就加氢甲酰基化而言,羰基氢化亚磷酸酯配合物和合成气体接触。亚磷酸酯和任选地,进一步的配位体可以以游离的形式与催化剂金属一起(作为盐或配合物)被引入到反应混合物中以就地产生活性催化剂种类。使用包含以上提到的亚磷酸酯配位体和催化剂金属的亚磷酸酯-金属配合物作为实际催化活性配合物的前体也是可能的。这些亚磷酸酯-金属配合物通过第4到10族适当的催化剂金属以元素的形式或以化学化合物的形式与亚磷酸酯配位体反应制备。
作为反应混合物中存在的另外的配位体,也可使用含磷配位体,例如膦,亚磷酸酯,亚膦酸酯或次磷酸酯。
这种配位体的例子是:
膦:三苯基膦,三(对-甲苯基)膦,三(间-甲苯基)膦,三(邻-甲苯基)膦,三(对-甲氧基苯基)膦,三(对-二甲基胺基苯基)膦,三环己基膦,三环戊基膦,三乙基膦,三(1-萘基)膦,三苄基膦,三正丁基膦,三叔丁基膦。
亚磷酸酯:三甲基亚磷酸酯,三乙基亚磷酸酯,三-正-丙基亚磷酸酯,三-异-丙基亚磷酸酯,三-正-丁基亚磷酸酯,三-异-丁基亚磷酸酯,三-叔-丁基亚磷酸酯,三(2-乙基己基)亚磷酸酯,三苯基亚磷酸酯,三(2,4-二-叔-丁基苯基)亚磷酸酯,三(2-叔-丁基-4-甲氧基苯基)亚磷酸酯,三(2-叔-丁基-4-甲基苯基)亚磷酸酯,三(对-羟甲苯基(kresyl))亚磷酸酯。另外,位阻亚磷酸酯配位体,特别是在EP-A-155,508,US-A-4,668,651,US-A-4,748,261,US-A-4,769,498,US-A-4,774,361,US-A-4,835,299,US-A-4,885,401,US-A-5,059,710,US-A-5,113,022,US-A-5,179,055,US-A-5,260,491,US-A-5,264,616,US-A-5,288,918,US-A-5,360,938,EP-A-472,071,EP-A-518,241和WO-A-97/20795中所描述的那些也是合适的配位体。
亚膦酸酯:甲基二甲氧基膦,苯基二甲氧基膦,苯基二苯氧基膦,2-苯氧基-2H-二苯并[c,e][1,2]氧杂磷杂环己烷(oxaphosphorin)和其衍生物,其中所有或一些氢原子已经被烷基和/或芳基或卤原子所取代,还有在WO-A-98/43935,JP-A-09-268152和DE-A-198 10 794和在德国专利申请DE-A-199 54 721和DE-A-199 54 510中描述的配位体。
常用的次磷酸酯,特别是在US-A-5,710,344,WO-A-95/06627,US-A-5,360,938或JP-A-07-082281中描述那些。例子是二苯基(苯氧基)膦和其衍生物,其中所有或一些氢原子已经被烷基和/或芳基或卤原子替换,二苯基(甲氧基)膦和二苯基(乙氧基)膦。
本发明的亚磷酸酯和亚磷酸酯-金属配合物可以用于烯烃加氢甲酰基化的方法以形成相应的醛,烯烃优选具有2-25个碳原子的那些。这里,优选使用具有作为催化剂前体的过渡族第8族金属的亚磷酸酯配合物。
通常,每摩尔过渡族第8族金属使用1-500mol,优选1-200mol,更优选2-50mol本发明的亚磷酸酯。新的亚磷酸酯配位体可以在任何时间点添加到反应中以保持游离配位体的浓度恒定。
反应混合物中金属的浓度是在1ppm-1000ppm的范围,优选在5ppm-300ppm的范围,以反应混合物的总重量为基础。
使用本发明的亚磷酸酯或相应的金属配合物进行的加氢甲酰基化反应通过已知的方法进行,例如,在J.FALBE,“New Syntheses withCarbon Monoxide”,Springer Verlag,柏林,Heidelberg,纽约,95页及其以下,(1980)中所描述的。烯烃化合物在催化剂存在的条件下与CO和H2(合成气体)反应形成具有多一个碳原子的醛。
使用本发明的亚磷酸酯或亚磷酸酯-金属配合物进行的加氢甲酰基化方法的反应温度优选40℃-180℃的范围,更优选75℃-140℃的范围。加氢甲酰基化进行的压力优选1-300bar的合成气体,更优选10-64bar。氢与一氧化碳(H2/CO)的摩尔比率优选为10/1-1/10,更优选1/1-2/1。
催化剂或配位体作为在包含初始原料(烯烃和合成气体)和产物(醛,醇,在过程中形成的高沸点物)的加氢甲酰基化混合物中均相溶解。任选地可以另外使用溶剂。
由于它们的高分子量,本发明的亚磷酸酯具有低挥发性。因此它们可以容易地从更具挥发性的反应产物中分离。它们在常规有机溶剂中具有足够好的溶解性。
加氢甲酰基化的初始原料是具有2-25个碳原子和末端或内部C=C双键的烯烃或烯烃的混合物。它们可以是直链的,支链的或具有环状结构,也可以具有多个烯键不饱和基团。例子是丙烯;1-丁烯,顺-2-丁烯,反-2-丁烯,异丁烯,丁二烯,C4-烯烃混合物;C5-烯烃,例如1-戊烯,2-戊烯,2-甲基-1-丁烯,2-甲基-2-丁烯,3-甲基-1-丁烯;C6-烯烃,例如1-己烯,2-己烯,3-己烯,在丙烯的二聚中形成的C6-烯烃混合物(二丙烯);C7-烯烃,例如1-庚烯,还有正-庚烯类,2-甲基-1-己烯,3-甲基-1-己烯;C8-烯烃,例如1-辛烯,还有正-辛烯类,2-甲基庚烯类,3-甲基庚烯类,5-甲基-2-庚烯,6-甲基-2-庚烯,2-乙基-1-己烯,在丁烯的二聚中形成的C8-烯烃混合物(二丁烯);C9-烯烃,例如1-壬烯,还有正-壬烯类,2-甲基辛烯类,3-甲基辛烯类,在丙烯的三聚中形成的C9-烯烃混合物(三丙烯);C10-烯烃,例如正-十烯,2-乙基-1-辛烯;C12-烯烃,例如正-十二烯类,在丙烯的四聚或丁烯的三聚中形成的C12-烯烃混合物(四丙烯或三丁烯),C14-烯烃,例如正-十四烯类,C16-烯烃,例如正-十六烯类,在丁烯的四聚中形成的C16-烯烃混合物(四丁烯)和通过具有不同碳原子数(优选2-4)的烯烃的共低聚反应制备的烯烃混合物,任选地通过蒸馏分成具有相同数目或相似数目的原子的馏分后。同样可使用通过费-托合成法产生的烯烃或烯烃混合物和通过乙烯的低聚获得或通过易位反应(Methathesereaktionen)或调聚反应可获得的烯烃。
优选的初始原料通常是α-烯烃,例如丙烯,1-丁烯,2-丁烯,1-己烯,1-辛烯和丁烯(二丁烯,二-正-丁烯,二异丁烯,三丁烯)的二聚体和三聚体。
加氢甲酰基化可以连续或不连续进行。工业装置的例子是搅拌容器,泡罩塔,喷射式喷嘴反应器,管式反应器和回路反应器,其中部分可以串联和/或装有内件。
反应以一步或多步进行。形成的醛化合物和催化剂的分离可以通过常规方法进行,例如,分馏。工业上,这可以,例如,通过蒸馏,通过降膜式蒸发器或薄膜式蒸发器取得。当高沸点溶剂中的催化剂溶液从低沸点产物中分离时,这是特别有用的。已经分离的催化剂溶液可以用于进一步的加氢甲酰基化。当使用低烯烃(例如丙烯,丁烯,戊烯)时,对于产物通过气相从反应器排放也是可能的。
下面的例子解释了本发明。
实施例
所有的实施例使用标准Schlenk技术在保护气体下进行。溶剂使用前在合适的干燥剂上干燥。
氯代化合物A
氯代化合物A(2-氯-4H-1,3,2-苯并二氧杂磷杂环己-4-酮)购自Aldrich,Taufkirchen,并按照供给样使用。
氯代化合物B
氯代化合物B使用以BE 667036,Farbwerke Hoechst AG,1966;化学文摘65(1966) 13741d中的方法为基础的方法由2-羟基-1-萘甲酸制备。下面的描述解释了合成步骤。
2-羟基-1-萘甲酸与三氯化磷的反应
9.22g(0.049mmol)2-羟基-1-萘甲酸,200ml干燥的甲苯和0.48g(0.005mol)N-甲基-吡咯烷酮被放入250ml Schlenk管中。10.14g(0.073mol)三氯化磷被慢慢添加到该混合物中同时伴随着搅拌。Schlenk管被连接到装有气体流量计的废气管路后,反应混合物被小心加热到95℃并在该温度下保持5小时。为了后处理,反应混合物被过滤并在减压下除去滤液的溶剂。
产率:11.01g(44.6mmol),相当于理论的91.0%。
31P-NMR(甲苯-D8):δ150.9ppm
杯[4]芳烃双-O-酰基亚磷酸酯
1(非对映异构体的混合物)的制备
1.85ml己烷中的正-丁基锂(1.6mol/l,2.96mmol)溶液在室温下被慢慢添加到溶解于40ml THF中的1.0g(1.48mmol)对-叔-丁基双二甲氧基杯[4]芳烃I中。产生的溶液在室温下搅拌2小时。溶解于5ml THF中的0.75g(2.96mmol)3-氯-2,4-二氧杂-3-磷杂菲-1-酮(phosphaphenanthren-1-on)II随后通过针被逐滴添加。添加后发生了从无色到淡黄色的颜色的改变。溶液搅拌过夜。溶剂的蒸发产生了作为黄色固体的粗制二亚磷酸酯
1。产品通过溶于30ml CH2Cl2并通过Celite硅藻土助滤剂过滤纯化。在50℃下溶液的蒸发产生了作为淡黄的空气和湿度敏感的固体的
1。
产率:1.24g(1.26mol,85%):
m.p.278℃
在CDCl3中的1H-NMR(400.1MHz):□=0.51(s,18H,C(CH3)3);0.53(s,18H,C(CH3)3);0.92(s,18H,C(CH3)3);0.95(s,18H,C(CH3)3);3.10(d,4H,2J(HH)=12.8Hz,Ar-CH2-Ar);3.11(d,4H,2J(HH)=13.0Hz,Ar-CH2-Ar);3.68(s,6H,O-CH3);3.73(s,6H,O-CH3);4.26(d,4H,2J(HH)=12.4Hz,Ar-CH2-Ar);4.35(d,4H,2J(HH)=12.8Hz,Ar-CH2-Ar);6.11(d,2H,4J(HH)=2.4Hz,Ar-H);6.13(d,2H,4J(HH)=2.3Hz,Ar-H);6.38(d,2H,4J(HH)=2.3Hz,Ar-H);6.42(d,2H,4J(HH)=2.2Hz,Ar-H);6.55(d,2H,4J(HH)=2.2Hz,Ar-H);6.62(d,2H,4J(HH)=2.3Hz,Ar-H);6.63(d,4H,4J(HH)=2.3Hz,Ar-H);7.07-7.88(m,20H,Naph-H);8.96(d,2H,3J(HH)=8.0Hz,Naph-
H);899(d,2H,3J(HH)=7.9Hz,Naph-
H).在CDCl3中的13C-NMR(100.6MHz):□=30.48(s,6C,C(CH3)3);30.66(s,6C,C(CH3)3);31.30(s,6C,C(CH3)3);31.33(s,6C,C(CH3)3);32.06(s,4C,Ar-CH2-Ar);32.10(s,4C,Ar-CH2-Ar);33.82(s,2C,C(CH3)3);33.84(s,2C,C(CH3)3);33.85(s,2C,C(CH3)3);33.87(s,2C,C(CH3)3);61.01(s,2C,O-CH3);61.28(s,2C,O-CH3);118.49(s,4C,Naph-
C);124.79-129.50(m,40C,Ar-C和Naph-
C);129.87-146.21(m,48C,Ar-
C quart和Naph-
C quart)在CDCl3中的31P-NMR(81.0MHz):□=102.3,103.5,104.1,104.6EI-MS,m/z(%):1108(4)[M]+;892(5)[M+H-R]+;675(50)[M-2R]+.
元素分析:
C68H70O10P2(1109.25) 计算值:C 73.63 H 6.36 P 5.58
测试值:C 70.13 H 6.37 P 5.30
使用杯[4]芳烃双-O-酰基亚磷酸酯
1的1-辛烯的加氢甲酰基化
加氢甲酰化在安装有压力保持器,气体流量计和鼓泡搅拌器的Buddeberg-200ml-高压釜中进行。高压釜在氩气氛下充填10ml作为催化剂前体的[Rh(1,5-环辛二烯)acac](acac=乙酰丙酮酸根阴离子)形式的铑的0.604mM溶液,5ml作为GC-标准的甲苯和相应量的THF和杯[4]芳烃双-O-酰基亚磷酸酯
1。将15ml 1-辛烯引入到压力移液管(Druckpipette)中。反应溶液的总体积为56ml。通过用合成气(CO/H2=1∶1)吹扫来置换氩气氛围,之后,在搅拌(1500rpm)的同时,在30-33巴的合成气压力下将铑-配位体-混合物加热至100或120℃。在达到所需反应温度之后,将合成气体压力增加到40或50巴,并且在整个反应时间中,通过压力调节器保持恒定。在加入烯烃之后,借助Bronkhorst(NL)公司的Hitec气体流量计记录气体消耗。加氢甲酰基化试验的反应时间在每种情况下为3小时。然后,反应混合物冷却到室温,高压釜泄压,用氩气冲洗。2ml高压釜溶液中加入10ml戊烷,并用气相色谱分析,其中没有检测到可证实的烯烃氢化和醇形成。
表1:1-辛烯的加氢甲酰基化
铑∶二亚磷酸酯的摩尔比 | C9-醛,总量 | 直链C9-醛 | 支链C9-醛 | 正/异[mol%] | ||
产率[mol%] | 正-C9[mol%] | 异-C8[mol%] | 异-C7[mol%] | 异-C6[mol%] | ||
1∶1 | 83.3 | 53.4 | 35.1 | 7.3 | 4.2 | 1.15 |
1∶2 | 85.4 | 58.9 | 34.0 | 5.0 | 2.1 | 1.43 |
1∶10 | 46.0 | 59.2 | 39.0 | 1.5 | 0.3 | 1.45 |
n-C9=壬醛
异-C8=2-甲基辛醛
异-C7=2-乙基庚醛
异-C6=2-丙基己醛
正/异=壬醛/所有支链C9-醛总和的比率
Claims (14)
1.具有以下结构式I或II的亚磷酸酯,
其中R1,R2,R3和R4每一个独立选自单价取代或未取代的脂族的、脂环族的、芳族的、杂芳族的、混合脂族-脂环族的、混合脂族-芳族的、杂环的、混合脂族-杂环的具有1-50个碳原子的烃基,H,F,Cl,Br,I,-CF3,-CH2(CF2)jCF3,其中j=0-9,-OR9,-COR9,-CO2R9,-CO2M,-SR9,-SO2R9,-SOR9,-SO3R9,-SO3M,-SO2NR9R10,-NR9R10,-N=CR9R10,其中R9和R10各自独立选自H,单价取代或未取代的脂族的和芳族的具有1-25个碳原子的烃基,并且M是碱金属离子,形式上半碱土金属离子,铵离子或鏻离子,
或相邻的基团R1到R4一起形成稠合取代的或未取代的芳族的、杂芳族的、脂族的、混合芳族-脂族的或混合杂芳族-脂族的环系统;
Q是k价的取代或未取代的脂族的、脂环族的、混合脂族-脂环族的、杂环的、混合脂族-杂环的、芳族的、杂芳族的、混合脂族-芳族的具有1-50个碳原子的烃基,其中Q的脂族部分可以包含氧,硫和/或氮,
k是至少2并且在与Q相连的各个结构单元中的R1,R2,R3和R4可以彼此不同。
2.权利要求1中的亚磷酸酯,其中至少两个相邻的基团R1到R4一起形成稠合的芳族的,杂芳族的,脂族的,混合芳族-脂族的或混合杂芳族-脂族的环系统,其可以是未取代的或被选自下列的至少一个基团取代:脂族的、脂环族的、芳族的、杂芳族的、混合脂族-脂环族的、混合脂族-芳族的、杂环的、混合脂族-杂环的具有1-50个碳原子的烃基,F,Cl,Br,I,-CF3,-CH2(CF2)jCF3,其中j=0-9,-OR9,-COR9,-CO2R9,-CO2M,-SR9,-SO2R9,-SOR9,-SO3R9,-SO3M,-SO2NR9R10,-NR9R10或-N=CR9R10,其中R9,R10和M如权利要求1所定义。
3.权利要求1或2中的亚磷酸酯,其中Q是具有下式III的二价烃基
和R11,R12,R13,R14,R15,R16,R17和R18如权利要求1或2中所定义的R1到R4,
W是二价基团CR19R20,其中R19和R20如R9和R10所下的定义,
m=0-1并且
位置a和b代表连接点。
4.权利要求1到3中任何一项所要求的亚磷酸酯,其中Q是具有下式IV的杯[正]芳烃基团;
其中R21,R22和R23各自独立地选自取代或未取代的具有1-25个碳原子的脂族的和芳族的烃基,H,F,Cl,Br,I,-CF3,-CH2(CF2)jCF3,其中j=0-9,-OR24,-COR24,-CO2R24,-CO2M,-SR24,-SO2R24,-SOR24,-SO3R24,-SO3M,-SO2NR24R25,-NR24R25和-N=CR24R25,其中R24和R25如R9和R10所定义并且M是碱金属离子,形式上半碱土金属离子,铵离子或鏻离子,
或相邻的基团R21到R23一起形成稠合取代的或未取代的芳族的、杂芳族的、脂族的、混合芳族-脂族的或混合杂芳族-脂族的环系统;
Y是二价基团CR24R25或CR24R25-O-CR24R25,
n=3-6和
位置a代表连接点或代表OR24,其中R24和R25如上所定义。
5.包含元素周期表第4,5,6,7,8,9或10族金属和权利要求1到4任何一项中要求的一种或多种亚磷酸酯的亚磷酸酯-金属配合物。
6.权利要求5中要求的亚磷酸酯-金属配合物,其中金属是铑,铂,钯,钴或钌。
7.权利要求1到4任何一项中要求的亚磷酸酯或权利要求5或6中要求的亚磷酸酯-金属配合物在催化中的应用。
8.权利要求1到4任何一项中要求的亚磷酸酯或权利要求5或6中要求的亚磷酸酯-金属配合物在均相催化中的应用。
9.权利要求1到4任何一项中要求的亚磷酸酯或权利要求5或6中要求的亚磷酸酯-金属配合物在烯烃加氢甲酰基化方法中的应用。
10.权利要求9中要求的应用,其中存在进一步的含磷配位体。
11.烯烃加氢甲酰基化的方法,其包括在权利要求5或6中要求的亚磷酸酯-金属配合物存在的条件下单烯烃或单烯烃混合物与一氧化碳和氢的混合物的反应。
13.权利要求12中要求的制备亚磷酸酯的方法,其中两个不同取代的卤代二氧杂磷杂环己酮(2a)和(2b)在步骤(a)中合成,之后在步骤(b)(i)中顺序与二醇反应或在步骤(b)(ii)中顺序与二酸反应以产生不对称的亚磷酸酯。
14.制备权利要求5或6要求的亚磷酸酯-金属配合物的方法,其包括元素周期表第4,5,6,7,8,9或10族金属以元素的形式或以化学化合物的形式与权利要求1到4任何一项中要求的亚磷酸酯反应。
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DE10140083A DE10140083A1 (de) | 2001-08-16 | 2001-08-16 | Neue Phosphitverbindungen und deren Metallkomplexe |
DE10140083.7 | 2001-08-16 |
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EP (1) | EP1417212B1 (zh) |
JP (1) | JP4272986B2 (zh) |
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CN (1) | CN1310928C (zh) |
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DE (2) | DE10140083A1 (zh) |
ES (1) | ES2301680T3 (zh) |
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JP2005500384A (ja) | 2005-01-06 |
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US7009068B2 (en) | 2006-03-07 |
ATE388157T1 (de) | 2008-03-15 |
KR100869042B1 (ko) | 2008-11-17 |
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JP4272986B2 (ja) | 2009-06-03 |
DE50211846D1 (de) | 2008-04-17 |
CN1310928C (zh) | 2007-04-18 |
US20040236134A1 (en) | 2004-11-25 |
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