CA2278572A1 - Use of perfluoroalkyl substituted phosphorus compounds as ligands for homogeneous catalysis in supercritical carbon dioxide - Google Patents
Use of perfluoroalkyl substituted phosphorus compounds as ligands for homogeneous catalysis in supercritical carbon dioxide Download PDFInfo
- Publication number
- CA2278572A1 CA2278572A1 CA002278572A CA2278572A CA2278572A1 CA 2278572 A1 CA2278572 A1 CA 2278572A1 CA 002278572 A CA002278572 A CA 002278572A CA 2278572 A CA2278572 A CA 2278572A CA 2278572 A1 CA2278572 A1 CA 2278572A1
- Authority
- CA
- Canada
- Prior art keywords
- reaction
- process according
- catalyst
- phosphorus compounds
- hydrogenation
- 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.)
- Abandoned
Links
- 125000005010 perfluoroalkyl group Chemical group 0.000 title claims abstract description 27
- 150000003018 phosphorus compounds Chemical class 0.000 title claims abstract description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 7
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 6
- 239000003446 ligand Substances 0.000 title description 6
- 238000007172 homogeneous catalysis Methods 0.000 title description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- 239000011541 reaction mixture Substances 0.000 claims abstract description 25
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 16
- 150000001336 alkenes Chemical class 0.000 claims abstract description 14
- 150000004291 polyenes Chemical class 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000000376 reactant Substances 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 26
- 239000010948 rhodium Substances 0.000 claims description 25
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 19
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 11
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 238000006664 bond formation reaction Methods 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 5
- 150000003624 transition metals Chemical group 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000012429 reaction media Substances 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims 1
- 150000000475 acetylene derivatives Chemical class 0.000 claims 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 17
- 150000002466 imines Chemical class 0.000 abstract description 4
- 150000005840 aryl radicals Chemical class 0.000 abstract 1
- 239000000470 constituent Substances 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 abstract 1
- -1 aryl phosphorus compounds Chemical class 0.000 description 32
- 239000000243 solution Substances 0.000 description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 14
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 14
- 239000000306 component Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 239000012071 phase Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 8
- 239000012300 argon atmosphere Substances 0.000 description 8
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 235000014786 phosphorus Nutrition 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 101150041968 CDC13 gene Proteins 0.000 description 4
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000007689 inspection Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- VKCYHJWLYTUGCC-UHFFFAOYSA-N nonan-2-one Chemical compound CCCCCCCC(C)=O VKCYHJWLYTUGCC-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229910000064 phosphane Inorganic materials 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- INTYDOLPAWEEIL-UHFFFAOYSA-N 1-bromo-4-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)benzene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC1=CC=C(Br)C=C1 INTYDOLPAWEEIL-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007792 gaseous phase Substances 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229940090044 injection Drugs 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006263 metalation reaction Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000005538 phosphinite group Chemical group 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NVVZEKTVIXIUKW-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-8-iodooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCI NVVZEKTVIXIUKW-UHFFFAOYSA-N 0.000 description 1
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 101100433394 Arabidopsis thaliana ZPR4 gene Proteins 0.000 description 1
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000005922 Phosphane Substances 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000004695 complexes Chemical class 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- SBWAJHLQMFBNIN-UHFFFAOYSA-N dichloro(2-dichlorophosphanylethyl)phosphane Chemical compound ClP(Cl)CCP(Cl)Cl SBWAJHLQMFBNIN-UHFFFAOYSA-N 0.000 description 1
- BOUYBUIVMHNXQB-UHFFFAOYSA-N dicyclohexyl(2-dicyclohexylphosphanylethyl)phosphane Chemical compound C1CCCCC1P(C1CCCCC1)CCP(C1CCCCC1)C1CCCCC1 BOUYBUIVMHNXQB-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- WYURNTSHIVDZCO-SVYQBANQSA-N oxolane-d8 Chemical compound [2H]C1([2H])OC([2H])([2H])C([2H])([2H])C1([2H])[2H] WYURNTSHIVDZCO-SVYQBANQSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000003002 phosphanes Chemical class 0.000 description 1
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000007514 turning Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
-
- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
-
- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
-
- 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
-
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention relates to the use of phosphorus compounds containing one or more perfluoroalkyl chains of the general formula R1 [R1 = -(CH2)x(CF2)yE
(E=F, H, x = 0-4, y = 2-12)] as catalysts or constituents of catalysts in a reaction mixture consisting essentially of the reactants, the catalyst and carbon dioxide in the supercritical state (scCO2). It was found in particular that the introduction of perfluoroalkyl side chains R1 into the aryl radicals of insoluble or poorly soluble arylphosphorus compounds markedly improves their solubility in scCO2, so that, surprisingly, it even surpasses the solubility of alkylphosphorus compounds known to be soluble. The invention also relates to the use of such reaction mixtures for the chemoselective hydrogenation of polyenes to monoenes for the hydroformylation of olefins, for the enantioselective hydrogenation of imines and for C-C cross-linking reactions.
(E=F, H, x = 0-4, y = 2-12)] as catalysts or constituents of catalysts in a reaction mixture consisting essentially of the reactants, the catalyst and carbon dioxide in the supercritical state (scCO2). It was found in particular that the introduction of perfluoroalkyl side chains R1 into the aryl radicals of insoluble or poorly soluble arylphosphorus compounds markedly improves their solubility in scCO2, so that, surprisingly, it even surpasses the solubility of alkylphosphorus compounds known to be soluble. The invention also relates to the use of such reaction mixtures for the chemoselective hydrogenation of polyenes to monoenes for the hydroformylation of olefins, for the enantioselective hydrogenation of imines and for C-C cross-linking reactions.
Description
SMB
Use of perfluoroalkyl substituted phosphorus compounds as liaands for homogeneous catalysis in supercritical carbon dioxide The present invention relates to the use of phosphorus com-pounds containing one or more perfluoroalkyl chains of general formula R1 [R1 - - (CHz) X (CF2) YE (E = F, H, x = 0 - 4, y = 2 -12)] as catalysts or catalyst components in a reaction mix-ture essentially consisting of reactants, the catalyst and carbon dioxide in a supercritical state (scC02). In particular, it has been found that the introduction of perfluoroalkyl side chains R1 in the aryl residues of insoluble or poorly soluble aryl phosphorus compounds results in a significant improvement of their solubility in scCOz, which surprisingly even exceeds the solubility of alkyl phosphorus compounds known to be soluble. The invention further relates to the use of such reaction mixtures for the chemoselective hydrogenation of polyenes to monoenes, for the hydroformylation of olefins, for the enantioselective hydrogenation of imines and for C-C bond-forming reactions.
Carbon dioxide in a supercritical state (scC02) is a useful solvent for performing catalytic reactions because it is toxicologically and ecologically safe, in contrast to conven-tional organic solvents. A further property of scCOz is its being completely miscible with many gaseous reactants in a wide range of proportions, thus avoiding a limitation of the reaction rate by diffusion processes, as often occurs in gas/liquid phase reactions. Further, since the solvent proper-ties of scC02 vary with pressure and temperature, a separation ( CA 02278572 1999-07-19 of major or minor products from the reaction mixture is possi-ble in favorable cases when the external parameters are suita-bly chosen. A survey of catalytic reactions in scCOZ is found in Science 1995, 269, 1065.
The use of phosphorus compounds as catalysts or catalyst components in scCOz is described in EP 0 652 202 A1 for the synthesis of formic acid and its derivatives. However, a study published in J. Am. Chem. Soc. 1996, 118, 344, shows that only those phosphorus compounds having alkyl residues are effectice catalysts for this process while aryl phosphorus compounds cannot be employed due to their poor solubility in scCOz.
However, as compared to alkyl phosphorus compounds, aryl phosphorus compounds are characterized by their clearly lower sensitivity towards oxygen, and as a rule, they are considera-bly more readily synthesized so that their use would mean a significant simplification of the technical operation of catalytic processes. Also, aryl compounds represent the vast majority of chiral phosphorus compounds which are used as catalysts or catalyst components in asymmetric catalysis (H.
Brunner, W. Zettelmeier, Handbook of Enantioselective Cataly-sis, VCH, Weinheim, 1993).
The solubility of aryl phosphorus compounds in scC02 can be increased by partial or complete hydrogenation of the aryl residues to saturated alkyl groups (Tetrahedron Letters 1996, 37, 2813). This effect is small, however, and it is moreover associated with the already mentioned drawbacks of alkyl phosphorus compounds. Further, this method is connected with a high synthetic expenditure and cannot be transferred to aryl phosphorus compounds in general. The same article also sug-gests the addition of perfluoroalkyl alcohols to the reaction mixture, as a possibility for increasing the solubility. This method also leads to only a small improvement of the solubil-ity, and additionally makes it difficult to make use of the above mentioned advantages of scC02 due to the undesirable use of larger amounts of additives.
Thus, it has been the object of the present invention to provide a general method for increasing the solubility of aryl phosphorus compounds in scC02, so that they can be employed as catalysts or catalyst components in reaction mixtures essen-tially consisting of the reactants, the catalyst and scC02.
It has been found that the attachment of one or more per-fluoroalkyl groups R1 to phosphorus compounds is a general method for increasing their solubility in scCOz and for enabling their use as catalysts or catalyst components in reaction mixtures essentially consisting of the reactants, the catalyst and scC02. R1 is a residue of the general formula - (CHz)X(CFZ)YE (E = F, H, x = 0 - 4, y = 2 - 12) , residues R1 being preferred with E = F, x = 2 and y = 2-10, with y = 6-8 being particularly preferred.
In particular, it has been found that the introduction of perfluoroalkyl side chains R1 in the aryl residues of insoluble or poorly soluble aryl phosphorus compounds results in a significant improvement of their solubility in scCOz, which surprisingly even considerably exceeds the solubility of alkyl phosphorus compounds known to be soluble.
In addition, it has been found that the phosphorus compounds substituted with R1 can be employed as catalyst components for the chemoselective hydrogenation of polyenes to monoenes, for the hydroformylation of olefins in scC02, for the enantioselec-tive hydrogenation of imines and for C-C bond-forming reac-tions.
( CA 02278572 1999-07-19 Synthesis and properties of perfluoroalkyl substituted phos-phorus compounds:
The synthesis of phosphorus compounds containing at least one perfluoroalkyl chain of general formula R1 is described in the Application EP 0 633 062 A1. Aryl phosphorus compounds with fluorinated alkyl chains are also described in EP 0 646 590 A1. In the present invention, the synthetic route summarized in Scheme 1 was chosen for the synthesis of perfluoroalkyl substituted aryl phosphorus compounds.
Br R1 R1 R1 1. Mg 1. n-BuLi v \ 2. R1-1) Kat. \ 2. F~PCh \ P /
Hal I II : R2 = NEt2 Hal = Cl, Br, I RI = -(CHz~c(CFz)yE III : R2 = CI
R~
E=F,H,x=0-4,y=2-12 IV: R2= ~
1. n-BuLi 2. C~~Ch /
/ ~ \
P
/ I I \
Scheme 1: Synthetic route for perfluoroalkyl substituted aryl phosphorus compounds.
The number and position of substitutions as well as the length of the - (CHz) X- chain and of the perfluorinated chain - (CF2) Y-are variable in this synthesis. For the preferred form of R1 (x = 2, y = 6-8), the coupled products I were obtained from Grignard compounds produced by conventional methods and the commercially available iodides R1-I in the presence of a transition metal catalyst, preferably a copper compound (Table 1) .
Table l: Perfluoroalkyl substituted phenylhalides Ia-d and the major components of the main fractions isolated by distillation.
No.Formula bp. [a] Yield ProductRf(CHZ),R, Ar-Ar [C] [b]
(%] [%] (~lI%] [%]
la ~ ~ 102-105 30.3 87.4 6.0 -Br CHyCHpCFyCFyCFyCFyCFyCFyCFyCF3 Ib ~ 113-118 35.2 75.8 12.1 7.1 I
Br CHZCHZCFZCFzCF2CFZCF2CF3 Ic ~ 95-100 45.2 89.1 2.8 -~
Br Br Id \ 90-96 13.3 69.9 12.2 -I
[a] under oil-pump vacuum. [b] based on the product contained in the main fraction. Further fractions containing product are obtained. [c] Rf = (CFZ) YF
Metallation of the aryl halides, preferably with n-BuLi, followed by coupling to phosphorus compounds RzZPR33_Z (RZ - any alkyl or aryl residue or - R3, R3 - reactive group, e.g., halogen, NR22, OR2, z = 0-2), leads to the aryl phosphorus compounds II-V (Table 2) . Starting with compounds II and III, further phosphorus compounds can be synthesized, as illus-trated in Scheme 2. For example, formula VII represents the class of compounds called phosphinites, and the bridge -X- in VI and VII may be chiral or achiral.
Rt R.
Rt I \ X
1. metallation / ~ ~ \ I
\I ~X / \
P 2. AB/G ~ G I I
CI
Rt Rt (a) R~t Rt Rt 1 X \ \ x /
HO OH
I
\ Base ~ \
I I
Pcl Rt~ t VII
Scheme 2: Further methods for the synthesis of chiral and achiral aryl phosphorus compounds with perfluoroalkyl side chains, starting with compounds of type III. (a) Synthesis of bidentate phosphanes VI, (b) synthesis of bidentate phos-phinites VII. - (ABG = leaving group, e.g., Br, tosylate; -X-- chiral or achiral carbon linker).
The perfluoroalkyl substituted aryl phosphorus compounds can be used for the synthesis of metal complexes by conventional methods. The representative Examples VIII-X are summarized in Table 3, without any limitation being imposed by the selection of the metals or the types of complexes.
( CA 02278572 1999-07-19 Table 2: Perfluoroalkyl substituted phosphorus compounds III-V and their characteristic spectroscopical data.
No. Formula Yield [%] 83'P [a] [ppm]
I
P
III \ ~ \ ~ 43.0 81.3 F~3CBCHZCH2 CHZCHZCBF~3 F~3CgCHpCH
IV 53.0 -4.6 F~3CgCHyCH P HyCHpCgF~3 \ \
F,aCaCHzCHz CHZCHzC6F,3 I \
Va / ~ \ 44.3 -16.2 ~I I~
Ft3CsCHzCHz H=CHZC6F~3 F,~CaCHZCHz CHzCHzCsF~~
I \ /
Vb ~ 45.0 -14.2 ~I I~
F~~CeCHzCHz CHZCHZCBF,~
F~~CBCHZCHz CHZCHzCaF,3 Vc I / ~ ~ I 20.1 -12.2 P P
I I /
F~3CBCHz Hz CHzCHzC6F,~
F~3CeCHp HZ CHyCHyCeF~3 \ /
Vd I / ~ \ I 21.7 -36.7 P P
/ I \
/
F~3CeCHyCH2 CHyCHyCeF~3 (a] Chemical shift in 31P f 1H) spectrum, recorded in CDC13 or Frigen/CDZC12.
_ g Table 3: Metal complexes VIII-X with perfluoroalkyl substi-tuted phosphorus compounds as ligands and their characteristic spectroscopical data [a].
No.formula 8('3C;P~) 8(3'P) J 8('3Rh) [b]
[ppm] (ppm] [Hz] [ppm]
VIII[(IV)3RhCl] not determined51.1 188, not determined (dt) 38 36.2 142, (dd) 38 IXa[(Va)Rh(hfacac)]134.7 (m) 70.5 196 459 (d) IXb[(Vb)Rh(hfacac)]134.7 (m) 70.5 196 459 (d) IXc[(Vc)Rh(hfacac)]137.0 (m) 71.8 196 461 (d) IXd[(Vd)Rh(hfacac)]134.0 (m) 66.5 197 705 (d) X trans-[(Va)2RuCh]not determined43.9 - -[a] in THF-d8 or CDC13. [b] Cipeo designates the carbon atom of the aryl residue directly bound to the P atom.
Increase of solubility in scC02 The introduction of the perfluoroalkyl groups R1 in phosphorus compounds increases the solubility of the latter in scC02 to such an extent that they can be used as effective catalysts in scC02; this also applies to alkyl phosphorus compounds, but especially to aryl phosphorus compounds. Using the complexes [ {R4P (CHZ) ZPR4}Rh (hafac) ] IX (hfacac - hexafluoroacetylaceton-ate) as examples, this effect is described quantitatively in the following.
_O P
/R ~
''O
FsC ~ P
. CA 02278572 1999-07-19 formula IX:
a b c CHpCHyCFyCFyCFyCFpCFyCF3 CHyCHyCFyCFyCFpCFpCFyCFpCFyCF3 CHyCHyCFyCFyCFyCFyCFyCF3 R4 ~ I ~ I ~ I
d a f CHyCHyCFpCFyCFyCFpCFyCF3 R4 ~ I w The solubility of complexes IXa,b in scC02 was determined by UV
spectroscopy and compared with the solubility of the unsubsti-tuted parent compound [(dppe)Rh(hfacac)] IXe. IXe is not soluble even at a high density p corresponding to a high dissolving power of the scCOz (Angew. Chem. 1978, 90, 748) (T = 50°C, p = 110 bar, p = 0.75 g cm-3). With IXa and IXb, however, yellow-orange solutions are obtained already at low densities (T = 50 °C, p = 90 bar, p = 0.55 g cm-3). From the absorption bands of the UV spectra (see Figure 1), a satura-tion concentration of 6.3 x 10-5 M for IXa and 7.5 x 10-5 M for IXb can be estimated using the Lambert-Beer law and compara-tive data from THF solutions. For comparison, Figure 1 also shows the UV spectrum of complex IXf with the alkyl phosphorus compound 1,2-bis(dicyclohexylphosphino)ethane (dcpe). The solubility of IXf in scC02 is 1.1 x 10-5 M under identical conditions, i.e., lower than that of IXa and IXb by a factor of 5 and 7, respectively.
( CA 02278572 1999-07-19 1.B
1.4 i 1.2 b s ~.o O A
o.s b ' a , B
n o.s c a o.4 0.2 o.o _.. v.--:: , :.....___ Wavelength (nm) Figure 1: W spectra of saturated solutions of complexes IXa (A) and IXb (B) and IXf (C) in scC02 (T = 50°C, p = 90 bar, p = 0.55 g cm-3, layer thickness 12 mm).
As the density of the supercritical phase increases, the solubility of perfluoroalkyl substituted phosphorus compounds is further increased. At a density of p = 0.75 g cm-3 (T = 50°C, p = 110 bar), for example, 158 mg of IXa completely dissolved in a high pressure cell (V = 17.3 cm-3), so that a value of 4.4 x 10-3 M can be estimated as the lower limit of solubility under such conditions. Thus, the solubility of IXa is at least 150 times higher than the maximum solubility of 0.03 x 10-3 M (T = 50°C, p = 345 bar) found by Burk et al. in J. Am. Chem. Soc. 1995, 117, 8277, for the alkyl phosphorus complex [ (Duphos) Rh (r)'-C8H12) ] '.
Use of perfluoroalkyl substituted phosphorus compounds as catalysts or catalyst components in scC02.
Thus, the introduction of a perfluoroalkyl side chain of general formula I converts the insoluble parent compound [(dppe)Rh(hfacac)] IXe to a perfluoroalkyl substituted aryl ~
phosphorus compound IXa which is not only soluble in scC02, but surprisingly even has a solubility which is significantly higher than that of known soluble alkyl phosphorus compounds.
Thus, aryl phosphorus compounds, which are characterized by a generally higher stability towards oxygen and thus an easier handling as compared to alkyl phosphorus compounds, become available for use as catalysts or catalyst components in scCOz.
For example, compounds IV are perfluoroalkyl substituted, scC02-soluble analogues of triphenylphosphine (TPP), which is widely employed as a catalyst or catalyst component in organic solvents. Compounds V are analogues of the bidentate ligand 1,2-bis(diphenylphosphino)ethane (dppe), which is also often used.
scC02-soluble catalysts which consist of perfluoroalkyl substi-tuted aryl phosphorus compounds and a transition metal can be formed in situ from suitable metal-containing precursor com-plexes and the phosphorus compounds, or preformed complexes such as VIII-X can be used. Examples of possible transition metal components include Ni, Pd, Pt, Co, Rh, Ir, Fe, Ru, Os, Ti, W, Mo, and compounds of such metals. Examples of catalytic processes include hydrogenations, oxidations, C-C bond-forming reactions and polymerizations. The examples described in the following demonstrate the potential of these catalysts in scC02, without any limitation of possible applications being imposed thereby. In particular, the example of the hydroformy-lation demonstrates the critical positive influence of the perfluoroalkyl chain R1.
a) Chemoselective hydrogenation of polyenes to monoenes The chemoselective hydrogenation of polyenes to monoenes in scC02 in the presence of catalysts based on perfluoroalkyl substituted aryl phosphorus compounds is conveniently per-formed by heating a mixture of the substrate, HZ and compressed COZ in a high pressure reactor to a temperature above the critical point of the mixture. The chemoselective hydrogena-tion of polyenes in scCOz in the presence of perfluoroalkyl substituted phosphorus compounds can be performed at tempera-tures from 30 °C, preferably between 40 °C and 100 °C and at H2 partial pressures of between 1 and 100 bar, preferably between 1 and 50 bar. The total pressure ranges between 100 to 300 bar, preferably between 180 and 250 bar. The catalyst, for example, IXa/NEt3, is added to this mixture. The progress of the reaction can be followed by means of the decrease in pressure due to H2 consumption. When the reaction is performed in scC02, the tedious and solvent-intensive processing of the reaction mixture can be avoided; for example, the hydrocarbons are collected in a practically pure form by simple condensing in a cooling trap. Exemplified by the hydrogenation of iso-prene, it was shown that IXa in scCOz achieves selectivities for the formation of the monounsaturated products comparable to those of the related catalyst [ (PhzP (CHZ) 3PPh2}Rh (r~3-CeHll) ] in organic solvents (Table 4). The proportion of 3-methylbutene-1 is even somewhat higher in scCOz than in conventional solvents.
Table 4: Product ratios in the chemoselective hydrogenation of isoprene in organic solvents and in scC02.
2-methyl- 2-methyl- 2-methyl- 3-methyl-butane butene-1 butene-2 butene-1 reaction medium: 11.8% 20.8% 67.2% 0.1 DMSO/quinuclidine; T= 80 °C;
p(H2) = 6 bar; cat.: 0.5 mole [f PhzP(CH2)3PPh~}Rh(r~3-C8H")]
reaction medium: scCO~/NEt3; 10.3% 28.7% 53.8% 7.7%
T = 40 °C, p(H2) = 45 bar; cat.:
0.08 mole % IXa (Example 8) b) Hydroformylation of 1-octene The cobalt catalyzed hydroformylation in scCOz without the addition of a phosphorus component has been described in US
5,198,589. However, in common solvents, rhodium complexes with phosphorus ligands have many advantages over cobalt catalysts in hydroformylations and are therefore increasingly used in technology (B. Cornils, W.A. Herrmann (eds.), Applied Homoge-neous Catalysis with Organometallic Compounds, Vol. 1, VCH, 1996, p. 7f). However, the transfer of the catalyst system Rh/TPP, which is technically established in organic solvents, to the use in scC02 fails due to the insolubility of the active species in this medium. Until the supercritical state is reached, the reaction proceeds to a small extent due to the solubility of the catalyst in the olefin. At the critical point, the catalyst becomes insoluble; the supercritical phase consisting of the olefin and COZ is then colorless, and no further conversion of the olefin takes place (Example 10).
In contrast, with the perfluoroalkyl substituted TPP analogue IV, the rhodium-catalyzed hydroformylation of olefins proceeds smoothly in scCOz (Example )), the solubility of the catalyti-cally active species under these conditions being indicated by an intense yellow color of the supercritical phase. Under supercritical conditions, a conversion of 92% and an n/iso ratio of 4.6 is achieved in the hydroformylation of 1-octene to 1-nonanal and 2-nonanal using a Rh/IV catalyst. The corre-sponding values for the control experiment with unsubstituted TPP (Example 10) are 26% and 3.5, respectively. This example demonstrates the importance of the perfluoroalkyl chains to the use of the aryl phosphanes as catalysts or catalyst compo-nents in scCOz .
The hydroformylation of olefins in scC02 in the presence of catalysts containing perfluoroalkyl substituted phosphorus compounds is conveniently performed by heating a mixture of the catalyst, the olefin, CO, HZ and COZ in a high pressure reactor to a temperature above the critical point of the mixture. The rhodium-catalyzed hydroformylation of olefins in the presence of perfluoroalkyl substituted phosphorus com-pounds can be performed at temperatures from 30°C, preferably between 40°C and 100°C, and at CO and HZ partial pressures of between 1 and 120 bar, preferably between 1 and 60 bar. The total pressure ranges between 100 and 300 bar, preferably between 180 and 250 bar.
Example 1:
Preparation of 1-bromo-4-(1H,1H,2H,2H-perfluorooctyl)benzene (Ia) In a 500 ml three-necked flask equipped with a reflux con-denser, bubble counter and dropping funnel, 4.30 g (0.18 mol) of Mg turnings were added to 15 ml of Et20, and then 40.5 g (0.17 mol) of 1,4-dibromobenzene in 75 ml of EtzO was added dropwise. The resulting Grignard solution was stirred at room temperature for 3 d, the excess Mg was filtered off, and the content of the Grignard solution determined by titration (1.85 M, 94.9$).
To a solution of 43.8 g (92.5 mmol) of 1H,1H,2H,2H-perfluoro-octyl iodide and 2 spatula-full of [ (r~'-C8H12) CuCl] in 20 ml of THF was added dropwise 47.5 ml (87.9 mmol) of the previously prepared Grignard solution at 5°C. The color of the reaction mixture turned from yellow to brown, and a precipitate formed.
The mixture was diluted with 100 ml of THF and 100 ml of Et20 and heated to reflux for 4 h. After cooling, the reaction solution was hydrolyzed with 300 ml of saturated NH4C1 solu-tion. The blue aqueous phase was partitioned with 3 x 50 ml of Et20, and the combined organic phases were washed with 2 x 40 ml of H20 and dried over Na2S04. After removing the solvent, a light-brown, highly viscous raw product was ob-~
tained, which was fractionally distilled under oil pump vacuum through a Vigreux column (length: 19 cm, diameter: 16 mm). At a boiling temperature of 102-105 °C, 15.3 g of a colorless oil was collected, which contained 87.4 Ia according to a GC
analysis. An analytically pure sample could be obtained by preparative GC.
GC/mass m/z (~) 502 (55) [M'+] , 423 (15) [M'+- ('9Br) ] , 169 spectrum (EI) : (100) [M'+-CHZC6Fla]
elemental calc.: C: 33.42 H: 1.60 Br: 15.88 F: 49.09 analysis: found: C: 33.55 H: 1.70 Br: 15.97 F: 48.69 In an analogous way, compounds Ia-d as listed in Table 1 were prepared.
Example 2:
Preparation of di-(4-(1H,1H,2H,2H-perfluorooctyl)phenyl]-chlorophosphane (III) 8.77 g (17.4 mmol) of Ia was dissolved in 50 ml of Et20, and ml of n-BuLi (1.7 M in hexane) was slowly added dropwise to this solution at -50°C under an argon atmosphere whereupon the turbid solution became intensely yellow. Subsequently, the solution, which had warmed up to 0°C, was added dropwise to a solution of 1 . 51 g of C12PNEt2 ( 8 . 6 mmol ) in 20 ml of THF . The mixture was stirred in an ice bath at 0 °C over night, where-upon a precipitate formed. After filtration, the clear reac-tion solution was treated with gaseous HC1 with stirring at room temperature for about 30 minutes. After a few minutes already, a colorless precipitate formed, which was redissolved in the course of the reaction. For degassing the solution, it was freezed out in a nitrogen bath, evacuated by means of an oil pump, and rethawed under an argon atmosphere. In doing so, a precipitate again formed, which was filtered off. The fil-~
trate was concentrated under vacuum to about half its original volume and maintained at -20°C over night for crystallization.
Filtering, washing twice with Et20 and drying under high vacuum afforded 3.38 g of III as colorless crystals.
mass spectrum (EI) m/z (%) 912 (100) [M'+]
Example 3:
Preparation of tri-[3-(1H,1H,2H,2H-perfluorooctyl)phenyl]phos-phane (IV) To 3.85 g (6.88 mmol) of Ic in 10 ml of Et20 was added dropwise 4.1 ml of n-BuLi (1.7 M in hexane) in 10 ml of Et20 at -25°C
under an argon atmosphere within 35 minutes . The yellow solu-tion obtained was briefly warmed to 0°C, and then 284 mg (2.06 mmol) of PC13 in 10 ml of EtzO was added dropwise at -10°C within 20 min, whereupon a precipitate appeared. After min of stirring at room temperature, the reaction mixture was hydrolyzed with 20 ml of saturated NHQC1 solution. The aqueous phase was extracted with 3 x 20 ml of Et20, and the combined organic phases were first washed with 2 x 10 ml of H20 and then dried over Na2S04. Evaporating the solvent afforded a light-brown solid which was recrystallized from 10 ml of a THF/MeOH mixture to yield 1.50 g of a colorless solid, which contained 94.4% IV according to a GC analysis.
mass spectrum m/z (%) 1300 (100) [M"]
(EI) Example 4:
Preparation of 1,2-bis(di-~4-(1H,1H,2H,2H-perfluorooctyl)-phenyl~phosphino]ethane (Va) To 1.61 g (2.80 mmol) of Ia in 10 ml of Et20 was added dopwise 1.75 ml of n-BuLi (1.7 M in hexane) in 5 ml of Et20 at -35°C
under an argon atmosphere within 10 min. The yellow solution obtained was briefly warmed to 0°C, and then 0.15 g (0.67 mmol) of 1,2-bis(dichlorophosphino)ethane in 7 ml Et20 was added dropwise at -23°C within 25 min. After 10 min of stirring at room temperature, the reaction mixture was hydro-lyzed with 10 ml of saturated NHQC1 solution, the aqueous phase was extracted with 2 x 10 ml of EtzO, and the combined organic phases were dried over Na2S04. The solvent was removed, and recrystallization of the raw product from 2-3 ml of THF/MeOH
afforded 0.56 g of a colorless solid, which contained 93.1% Va according to a GC analysis.
mass m/z (%) 1782 (100) [M'+] , 1754 (15) [M'+-CHzCHz] , spectrum 1327 (30) [M'+- (P-C6H4-CHzCH2C6F13+H) ] , 1313 (10) (EI) : [M'+- (P-C6H4-CHzCHzC6F13+CH3) ] , 1300 (25) [M'+- (P-C6H4-CHzCH2C6F13+CzH4) ] , 877 (35) [M~+- (-CHZCHZ-P- (C6H4-CH2CHzC6F13) z) ]
elemental calc.: C: 39.08 H: 2.04 F: 55.41 P: 3.48 analysis: found: C: 39.04 H: 2.02 F: 55.28 P: 3.47 In an analogous way, compounds Va-d as listed in Table 1 were prepared.
Example 5:
Preparation of [(IV)3RhCl] (VIII) A solution of 520 mg (0.40 mmol) of IV in 3 ml of THF was added dropwise to a solution of 17 mg (0.02 mmol) of [((~z-C8H14) zRh (~,-C1 ~2] in 3 ml THF under an argon atmosphere within minutes, whereupon the previously orange-yellow colored solution turned dark red. It was stirred at room temperature for 30 min, and after removing the solvent, a dark-red solid remained which was recrystallized from 2 ml of a THF/MeOH
mixture. After drying the crystals under high vacuum, 156.0 mg of VIII was obtained as a dark-red solid.
Example 6:
Preparation of [(Ya)Rh(hfacac)] (IXa):
To a solution of 84.5 mg (0.20 mmol) of [ (r~4-C8H12) Rh(hfacac) ]
in 10 ml of THF was added dropwise 387 mg (0.20 mmol) of Va in 10 ml of THF at -78°C under an argon atmosphere. After comple-tion of the addition, the reaction solution was slowly warmed to room temperature, and after about 20 minutes of stirring at room temperature, a deep red-brown solution was obtained. The solvent was removed under oil pump vacuum, and the residual red-brown solid (0.52 g) was recrystallized from 5 ml of an MeOH/THF mixture. After 3 d of drying under high vacuum with slight heating, 0.31 g of the pure complex IXa was obtained.
mass spectrum m/z (~) 2092 (10) [M"]
(EI): (direct injection) elemental calc.: C: 36.16 H: 1.78 F: 52.65 P: 2.96 analysis: found: C: 36.03 H: 1.85 F: 52.53 P: 2.95 In an analogous way, compounds IXa-d as listed in Table 1 were prepared.
Example 7:
Preparation of trans- [ (Va) ZRuCl2] (X) To a suspension of 0.99 g of Ya (0.55 mmol) in 120 ml of ethanol was added a solution of 68.2 mg of RuCl3 hydrate (35-40% Ru, 0.23 mmol) in 4 ml of degassed water under an argon atmosphere. Subsequently, the mixture was heated to reflux for 2 h, whereupon the previously green colored suspension turned light yellow. After filtration, removing the solvent and drying under high vacuum, 0.74 g of X was obtained.
Example 8:
Chemoselective hydrogenation of isoprene in scC02 with IXa as a catalyst:
5.94 g of isoprene (87 mmol) was charged in a pressure reactor (V = 100 ml) flushed with Hz, and hydrogen was used to adjust a pressure of 45 bar (about 200 mmol) at room temperature. Then, 67 g of COZ was supplied to the autoclave by means of a com-pressor, upon which a total pressure of 135 bar resulted in the reactor. The reactor was then heated to +40. degree.C, the transi-tion of the mixture to the supercritical range being ensured by visual monitoring (inspection glass). A solution of 190 mg of the Rh complex IXa (0.09 mmol) in 2.3 g of NEt3 was then introduced in the pressure reactor by means of a sample injec-tion system, whereupon the previously colorless supercritical phase turned orange-yellow. After 19 h, the pressure was released, and the hydrocarbons were condensed in a cooling trap cooled with acetone/dry ice. The product distribution was established by GC.
. CA 02278572 1999-07-19 Example 9:
Hydroformylation of 1-octene in scCOz with [ (~4-C8H12)Rh(hfaCaC) ] /IV as a catalyst:
17.4 mg of [ (r~4-CeHl2)Rh(hfacac) ] (0.05 mmol) and 352 mg of IV
(0.27 mmol) were charged as solids to a pressure reactor (V =
20 ml) flushed with argon, and 1.50 ml of 1-octene (9.60 mmol) was added. Subsequently, a 1:1 CO/HZ mixture of gases was added at room temperature under a pressure of up to 60 bar. After about 20 minutes, 13.6 g of COz was supplied by means of a compressor. Then, the reaction mixture was heated to 60°C
which gave rise to a total pressure of 220 bar. The super-critical phase formed was homogeneous and had a yellow color.
Within the reaction time of 19 h, the internal pressure de-creased by about 25 bar to 190 bar. A 1H NMR spectroscopical analysis performed immediately after reaching the supercriti-cal state and 19 h later showed that a conversion of 92% to 1-nonanal (n-aldehyde) and 2-nonanal (iso-aldehyde) had been achieved in the supercritical medium with an n/iso ratio of 4.6.
Example 10:
Attempted hydroformylation of 1-octene in scCOz with [(r~4-CBH12)Rh(hfacac) ] /TPP as a catalyst:
19.1 mg of [ (r~'-CeHl2)Rh(hfacac) ] (0.05 mmol) and 72.5 mg (0.28 mmol) of TPP were charged as solids to a pressure reac-tor (V = 20 ml) flushed with argon, and 1.50 ml (9.6 mmol) of 1-octene was added. Part of the solids dissolved in the sub-strate to form a red-brown solution. Then, 60 bar of a 1:1 CO/HZ mixture of gases was added at room temperature, and then, about 20 minutes later, 13.6 g of COz was supplied by means of a compressor. After the reaction mixture had been heated to 60°C, an internal pressure of 225 bar resulted and did not _ CA 02278572 1999-07-19 change any more in the further course of the process. The supercritical phase formed was colorless, and an insoluble solid was present. A 1H NMR spectroscopical analysis performed with a sample taken immediately after reaching the supercriti-cal state (visual monitoring) showed that a conversion of 26%
to 1-nonanal (n-aldehyde) and 2-nonanal (iso-aldehyde) had been achieved with an n/iso ratio of 3.5. After 18 h in the supercritical state, the pressure was released, and the prod-ucts and educts were isolated. Another analysis by 1H NMR
showed that no more aldehyde had been formed in the super-critical state.
Example 11:
This Example shows the applicability of the present method to the use of aryl phosphates:
Preparation of tris[4-(1H,1H,2H,2H-perfluorooctyl)phenyl]
phosphate (XI):
The aryl phosphate XI was obtained by analogy with Examples (1) and (3) according to Scheme 3.
OMe OH
1. vf~. F~~O. rctl ~ p~>
\ ~ LIICH~hICF~~F, \ ~ tOIU~
Itr~.GHn)C"Ol lat.>. -20'C
1NF.0'C-> I3'C (~t)t~~2)6F
3. B6ry, CH~O~
-7a'C ..> 21'C
GC/mass m/z (%) 1348 (25) [M'+]
spectrum (EI) elemental calc.: C: 37.41 H: 1.79 P: 2.30 analysis: found: C: 37.29 H: 1.88 P: 2.23 31P NMR: 8 128.5 (CDC13) Scheme 3: Synthesis of aryl phosphate XI and selected analyti-cal data.
The aryl phosphate XI was employed in the hydroformylation of 1-octene (conditions: T = 65°C, p(HZ/CO) - 20 bar, 1-octene:
[Rh]:[P] - 2175:1:10) by analogy with Example 9. An analysis by NMR spectroscopy and gas chromatography of the reaction mixture revealed a conversion of 50% after 7.5 h and a conver-sion of 98% (n/iso = 5.6, determined by 1H NMR) after 88 h.
Example 12:
This Example shows the applicability of the present method when using the reaction mixtures in the hydrogenation of polar double bonds, especially in the enantioselective hydrogenation of amines. The control experiment demonstrates the positive influence of the perfluoroalkyl residues.
The perfluorinated chiral ligand (XIIb) and the unsubstituted parent compound (XIIa) were prepared by known methods (P. von Matt et al., Tetrahedron: Asymmetry 1994, 5, 573), compound III being used instead of Ph2PCl in the synthesis of XIIb. The iridium complexes [ (XII) Ir (cod) ] [BPh4] were employed for the enantioselective hydrogenation of Ph(CH3)C=NPh in scC02 under the conditions summarized in Scheme 4; XIIb proved superior to its parent compound XIIa with respect to both activity and selectivity.
)'h H H
1V H2 (30 bar)) T= 40°C H N-Ph Ph-N H
P CH3 scC02, d= 0.75 g/mL ph C~ h~C h cat.: [(XII)Ir(cod)][BPhe]
reacction time Yield of amine ee (R) (GC) (HPLC) X~2: R = H 20 h ~ ~ % ...
40 h 83% 60%
XQb: R = F(CFp)s(CI-!2)2 20 h 96% fib°/.
Scheme 4: Use of perfluorinated ligands for the enantioselec-tive hydrogenation of imines in scC02.
Example 13:
This Example shows the applicability of the present method when using the reaction mixtures in C-C bond-forming reac-tions, especially in the polymerization of phenylacetylene.
Due to its non-linear optical and magnetic properties, polyphenylacetylene is an important polymeric material in materials technology (G. Costa, in: Comprehensive Polymer Science, Vol. 4, G. Allen, J.C. Bevington (eds.), Pergamon Press, Oxford, 1989, p. 155ff).
Under an Ar atmosphere (glove box), 7.0 mg (2.36 x 10-z mmol) of [ (r~4-C,HB) Rh (acac) ] (acac - acetylacetonate) was weighed together with 30 mg (2 . 31 x 10-z mmol) of [4-F (CF2) 6 (CH2) zC6H4] sP
(synthesis by analogy with that of IV) in a stainless steel high pressure reactor (V = 27 ml) equipped with an inspection glass, PTFE stirring bar, bores for temperature sensors, isolating valve and ball valve, and about 10 equivalents of NEt3 was added. A metering device with a gas tank was mounted to the ball valve of the autoclave by a Swagelok screw j oint and filled with 0.25 ml (2.27 mmol) of phenylacetylene.
Through the needle valve, COZ (20.9 g, d = 0.78 g~ml-1, 83 bar) was filled in the reactor by means of a compressor, and the reaction mixture was heated to 40-42°C with stirring, where-upon the pressure increased to 130-135 bar, and a homogeneous yellow phase was formed. The gas tank was filled with 150-180 bar of argon, the metering device was pressurized, the monomer was injected by opening the ball valve towards the reactor volume, and the metering device was repeatedly flushed with argon pressure. A spontaneous change in color to orange was observed, and after a few seconds already, an orange precipitate was deposited at the inspection glass of the autoclave. After two hours of stirring, the reactor was cooled to 0°C, and the pressure released, and then 20 ml of THF and 1 ml of glacial acetic acid were added under an argon atmos-phere, and the mixture was stirred over night. With vigorous stirring, the red solution was siphoned into a two-necked flask with 200 ml of MeOH for precipitation of the polypheny-lacetylene, and solid residues were isolated separately. After filtration and washing with MeOH and acetone, the product fractions were dried under oil pump vacuum.
overall yield: 213 mg (2.09 mmol, 92~), orange platelets (cis-transoidal) + red crystals (cis-cisoidal) in a weight ratio of 40:60 1H NMR, CDC13 8 6.93-6.91 (m, 3H, meta/para), 6.65-6.61 200.1 l~iz (m, 2H, ortho) , 5.82 (s, 1H, vinyl) (soluble fraction, 6~ie ~ 77-78~.
cis-transoidal PPA) Example 14:
This experiment shows the possibility of separating the cata-lyst from the product, exemplified by the hydroformylation of 1-octene.
14.4 mg (0.034 mmol) of [ (r~4-C8H12)Rh(hfacac) ] , 337 mg (0 .260 mmol) of [4-F (CFZ) 6 (CHz) zC6H4] 3P (synthesis by analogy with IV) and 10.8 g (96 mmol) of 1-octene were separately charged in a 275 ml autoclave with an inspection glass. After sealing the reactor, 20 bar of synthesis gas was added, and sufficiently CO2 was added by means of a compressor to give a total pressure of 120 bar at room temperature. Then, the mixture was heated to 65°C with stirring. A homogeneous yellow phase formed, and an internal pressure of about 210 bar re-sulted. After 24 h, an internal pressure of 190 bar was read.
The mixture was cooled down to room temperature to form a two-phase system consisting of a colorless gaseous phase and a yellow liquid phase.
After another 24 h, COZ was removed by carefully releasing the pressure through a valve provided at the reactor head, until the volumes of the liquid and gaseous phases present in the reactor were approximately equal. Then, after closing the valve, the mixture was heated to 60°C. During this, the volume of the liquid phase decreased, and an internal pressure of 100 bar was reached. Then, a constant amount (about 10 1/min) of the upper phase was removed through the top valve and passed through a separator. In order to keep the pressure within the reactor constant, COZ was constantly added through a valve provided at the bottom of the reactor. After about 15 minutes, 4 ml of a colorless liquid had gathered in the sepa-rator. An analysis by 1H NMR showed that 95% of the mixture consisted of 1-nonanal and 2-nonanal (n/iso = 2.5). By atom absorption spectroscopy (AAS), a Rh content of 9 ppm was determined in the separated mixture of aldehydes.
Use of perfluoroalkyl substituted phosphorus compounds as liaands for homogeneous catalysis in supercritical carbon dioxide The present invention relates to the use of phosphorus com-pounds containing one or more perfluoroalkyl chains of general formula R1 [R1 - - (CHz) X (CF2) YE (E = F, H, x = 0 - 4, y = 2 -12)] as catalysts or catalyst components in a reaction mix-ture essentially consisting of reactants, the catalyst and carbon dioxide in a supercritical state (scC02). In particular, it has been found that the introduction of perfluoroalkyl side chains R1 in the aryl residues of insoluble or poorly soluble aryl phosphorus compounds results in a significant improvement of their solubility in scCOz, which surprisingly even exceeds the solubility of alkyl phosphorus compounds known to be soluble. The invention further relates to the use of such reaction mixtures for the chemoselective hydrogenation of polyenes to monoenes, for the hydroformylation of olefins, for the enantioselective hydrogenation of imines and for C-C bond-forming reactions.
Carbon dioxide in a supercritical state (scC02) is a useful solvent for performing catalytic reactions because it is toxicologically and ecologically safe, in contrast to conven-tional organic solvents. A further property of scCOz is its being completely miscible with many gaseous reactants in a wide range of proportions, thus avoiding a limitation of the reaction rate by diffusion processes, as often occurs in gas/liquid phase reactions. Further, since the solvent proper-ties of scC02 vary with pressure and temperature, a separation ( CA 02278572 1999-07-19 of major or minor products from the reaction mixture is possi-ble in favorable cases when the external parameters are suita-bly chosen. A survey of catalytic reactions in scCOZ is found in Science 1995, 269, 1065.
The use of phosphorus compounds as catalysts or catalyst components in scCOz is described in EP 0 652 202 A1 for the synthesis of formic acid and its derivatives. However, a study published in J. Am. Chem. Soc. 1996, 118, 344, shows that only those phosphorus compounds having alkyl residues are effectice catalysts for this process while aryl phosphorus compounds cannot be employed due to their poor solubility in scCOz.
However, as compared to alkyl phosphorus compounds, aryl phosphorus compounds are characterized by their clearly lower sensitivity towards oxygen, and as a rule, they are considera-bly more readily synthesized so that their use would mean a significant simplification of the technical operation of catalytic processes. Also, aryl compounds represent the vast majority of chiral phosphorus compounds which are used as catalysts or catalyst components in asymmetric catalysis (H.
Brunner, W. Zettelmeier, Handbook of Enantioselective Cataly-sis, VCH, Weinheim, 1993).
The solubility of aryl phosphorus compounds in scC02 can be increased by partial or complete hydrogenation of the aryl residues to saturated alkyl groups (Tetrahedron Letters 1996, 37, 2813). This effect is small, however, and it is moreover associated with the already mentioned drawbacks of alkyl phosphorus compounds. Further, this method is connected with a high synthetic expenditure and cannot be transferred to aryl phosphorus compounds in general. The same article also sug-gests the addition of perfluoroalkyl alcohols to the reaction mixture, as a possibility for increasing the solubility. This method also leads to only a small improvement of the solubil-ity, and additionally makes it difficult to make use of the above mentioned advantages of scC02 due to the undesirable use of larger amounts of additives.
Thus, it has been the object of the present invention to provide a general method for increasing the solubility of aryl phosphorus compounds in scC02, so that they can be employed as catalysts or catalyst components in reaction mixtures essen-tially consisting of the reactants, the catalyst and scC02.
It has been found that the attachment of one or more per-fluoroalkyl groups R1 to phosphorus compounds is a general method for increasing their solubility in scCOz and for enabling their use as catalysts or catalyst components in reaction mixtures essentially consisting of the reactants, the catalyst and scC02. R1 is a residue of the general formula - (CHz)X(CFZ)YE (E = F, H, x = 0 - 4, y = 2 - 12) , residues R1 being preferred with E = F, x = 2 and y = 2-10, with y = 6-8 being particularly preferred.
In particular, it has been found that the introduction of perfluoroalkyl side chains R1 in the aryl residues of insoluble or poorly soluble aryl phosphorus compounds results in a significant improvement of their solubility in scCOz, which surprisingly even considerably exceeds the solubility of alkyl phosphorus compounds known to be soluble.
In addition, it has been found that the phosphorus compounds substituted with R1 can be employed as catalyst components for the chemoselective hydrogenation of polyenes to monoenes, for the hydroformylation of olefins in scC02, for the enantioselec-tive hydrogenation of imines and for C-C bond-forming reac-tions.
( CA 02278572 1999-07-19 Synthesis and properties of perfluoroalkyl substituted phos-phorus compounds:
The synthesis of phosphorus compounds containing at least one perfluoroalkyl chain of general formula R1 is described in the Application EP 0 633 062 A1. Aryl phosphorus compounds with fluorinated alkyl chains are also described in EP 0 646 590 A1. In the present invention, the synthetic route summarized in Scheme 1 was chosen for the synthesis of perfluoroalkyl substituted aryl phosphorus compounds.
Br R1 R1 R1 1. Mg 1. n-BuLi v \ 2. R1-1) Kat. \ 2. F~PCh \ P /
Hal I II : R2 = NEt2 Hal = Cl, Br, I RI = -(CHz~c(CFz)yE III : R2 = CI
R~
E=F,H,x=0-4,y=2-12 IV: R2= ~
1. n-BuLi 2. C~~Ch /
/ ~ \
P
/ I I \
Scheme 1: Synthetic route for perfluoroalkyl substituted aryl phosphorus compounds.
The number and position of substitutions as well as the length of the - (CHz) X- chain and of the perfluorinated chain - (CF2) Y-are variable in this synthesis. For the preferred form of R1 (x = 2, y = 6-8), the coupled products I were obtained from Grignard compounds produced by conventional methods and the commercially available iodides R1-I in the presence of a transition metal catalyst, preferably a copper compound (Table 1) .
Table l: Perfluoroalkyl substituted phenylhalides Ia-d and the major components of the main fractions isolated by distillation.
No.Formula bp. [a] Yield ProductRf(CHZ),R, Ar-Ar [C] [b]
(%] [%] (~lI%] [%]
la ~ ~ 102-105 30.3 87.4 6.0 -Br CHyCHpCFyCFyCFyCFyCFyCFyCFyCF3 Ib ~ 113-118 35.2 75.8 12.1 7.1 I
Br CHZCHZCFZCFzCF2CFZCF2CF3 Ic ~ 95-100 45.2 89.1 2.8 -~
Br Br Id \ 90-96 13.3 69.9 12.2 -I
[a] under oil-pump vacuum. [b] based on the product contained in the main fraction. Further fractions containing product are obtained. [c] Rf = (CFZ) YF
Metallation of the aryl halides, preferably with n-BuLi, followed by coupling to phosphorus compounds RzZPR33_Z (RZ - any alkyl or aryl residue or - R3, R3 - reactive group, e.g., halogen, NR22, OR2, z = 0-2), leads to the aryl phosphorus compounds II-V (Table 2) . Starting with compounds II and III, further phosphorus compounds can be synthesized, as illus-trated in Scheme 2. For example, formula VII represents the class of compounds called phosphinites, and the bridge -X- in VI and VII may be chiral or achiral.
Rt R.
Rt I \ X
1. metallation / ~ ~ \ I
\I ~X / \
P 2. AB/G ~ G I I
CI
Rt Rt (a) R~t Rt Rt 1 X \ \ x /
HO OH
I
\ Base ~ \
I I
Pcl Rt~ t VII
Scheme 2: Further methods for the synthesis of chiral and achiral aryl phosphorus compounds with perfluoroalkyl side chains, starting with compounds of type III. (a) Synthesis of bidentate phosphanes VI, (b) synthesis of bidentate phos-phinites VII. - (ABG = leaving group, e.g., Br, tosylate; -X-- chiral or achiral carbon linker).
The perfluoroalkyl substituted aryl phosphorus compounds can be used for the synthesis of metal complexes by conventional methods. The representative Examples VIII-X are summarized in Table 3, without any limitation being imposed by the selection of the metals or the types of complexes.
( CA 02278572 1999-07-19 Table 2: Perfluoroalkyl substituted phosphorus compounds III-V and their characteristic spectroscopical data.
No. Formula Yield [%] 83'P [a] [ppm]
I
P
III \ ~ \ ~ 43.0 81.3 F~3CBCHZCH2 CHZCHZCBF~3 F~3CgCHpCH
IV 53.0 -4.6 F~3CgCHyCH P HyCHpCgF~3 \ \
F,aCaCHzCHz CHZCHzC6F,3 I \
Va / ~ \ 44.3 -16.2 ~I I~
Ft3CsCHzCHz H=CHZC6F~3 F,~CaCHZCHz CHzCHzCsF~~
I \ /
Vb ~ 45.0 -14.2 ~I I~
F~~CeCHzCHz CHZCHZCBF,~
F~~CBCHZCHz CHZCHzCaF,3 Vc I / ~ ~ I 20.1 -12.2 P P
I I /
F~3CBCHz Hz CHzCHzC6F,~
F~3CeCHp HZ CHyCHyCeF~3 \ /
Vd I / ~ \ I 21.7 -36.7 P P
/ I \
/
F~3CeCHyCH2 CHyCHyCeF~3 (a] Chemical shift in 31P f 1H) spectrum, recorded in CDC13 or Frigen/CDZC12.
_ g Table 3: Metal complexes VIII-X with perfluoroalkyl substi-tuted phosphorus compounds as ligands and their characteristic spectroscopical data [a].
No.formula 8('3C;P~) 8(3'P) J 8('3Rh) [b]
[ppm] (ppm] [Hz] [ppm]
VIII[(IV)3RhCl] not determined51.1 188, not determined (dt) 38 36.2 142, (dd) 38 IXa[(Va)Rh(hfacac)]134.7 (m) 70.5 196 459 (d) IXb[(Vb)Rh(hfacac)]134.7 (m) 70.5 196 459 (d) IXc[(Vc)Rh(hfacac)]137.0 (m) 71.8 196 461 (d) IXd[(Vd)Rh(hfacac)]134.0 (m) 66.5 197 705 (d) X trans-[(Va)2RuCh]not determined43.9 - -[a] in THF-d8 or CDC13. [b] Cipeo designates the carbon atom of the aryl residue directly bound to the P atom.
Increase of solubility in scC02 The introduction of the perfluoroalkyl groups R1 in phosphorus compounds increases the solubility of the latter in scC02 to such an extent that they can be used as effective catalysts in scC02; this also applies to alkyl phosphorus compounds, but especially to aryl phosphorus compounds. Using the complexes [ {R4P (CHZ) ZPR4}Rh (hafac) ] IX (hfacac - hexafluoroacetylaceton-ate) as examples, this effect is described quantitatively in the following.
_O P
/R ~
''O
FsC ~ P
. CA 02278572 1999-07-19 formula IX:
a b c CHpCHyCFyCFyCFyCFpCFyCF3 CHyCHyCFyCFyCFpCFpCFyCFpCFyCF3 CHyCHyCFyCFyCFyCFyCFyCF3 R4 ~ I ~ I ~ I
d a f CHyCHyCFpCFyCFyCFpCFyCF3 R4 ~ I w The solubility of complexes IXa,b in scC02 was determined by UV
spectroscopy and compared with the solubility of the unsubsti-tuted parent compound [(dppe)Rh(hfacac)] IXe. IXe is not soluble even at a high density p corresponding to a high dissolving power of the scCOz (Angew. Chem. 1978, 90, 748) (T = 50°C, p = 110 bar, p = 0.75 g cm-3). With IXa and IXb, however, yellow-orange solutions are obtained already at low densities (T = 50 °C, p = 90 bar, p = 0.55 g cm-3). From the absorption bands of the UV spectra (see Figure 1), a satura-tion concentration of 6.3 x 10-5 M for IXa and 7.5 x 10-5 M for IXb can be estimated using the Lambert-Beer law and compara-tive data from THF solutions. For comparison, Figure 1 also shows the UV spectrum of complex IXf with the alkyl phosphorus compound 1,2-bis(dicyclohexylphosphino)ethane (dcpe). The solubility of IXf in scC02 is 1.1 x 10-5 M under identical conditions, i.e., lower than that of IXa and IXb by a factor of 5 and 7, respectively.
( CA 02278572 1999-07-19 1.B
1.4 i 1.2 b s ~.o O A
o.s b ' a , B
n o.s c a o.4 0.2 o.o _.. v.--:: , :.....___ Wavelength (nm) Figure 1: W spectra of saturated solutions of complexes IXa (A) and IXb (B) and IXf (C) in scC02 (T = 50°C, p = 90 bar, p = 0.55 g cm-3, layer thickness 12 mm).
As the density of the supercritical phase increases, the solubility of perfluoroalkyl substituted phosphorus compounds is further increased. At a density of p = 0.75 g cm-3 (T = 50°C, p = 110 bar), for example, 158 mg of IXa completely dissolved in a high pressure cell (V = 17.3 cm-3), so that a value of 4.4 x 10-3 M can be estimated as the lower limit of solubility under such conditions. Thus, the solubility of IXa is at least 150 times higher than the maximum solubility of 0.03 x 10-3 M (T = 50°C, p = 345 bar) found by Burk et al. in J. Am. Chem. Soc. 1995, 117, 8277, for the alkyl phosphorus complex [ (Duphos) Rh (r)'-C8H12) ] '.
Use of perfluoroalkyl substituted phosphorus compounds as catalysts or catalyst components in scC02.
Thus, the introduction of a perfluoroalkyl side chain of general formula I converts the insoluble parent compound [(dppe)Rh(hfacac)] IXe to a perfluoroalkyl substituted aryl ~
phosphorus compound IXa which is not only soluble in scC02, but surprisingly even has a solubility which is significantly higher than that of known soluble alkyl phosphorus compounds.
Thus, aryl phosphorus compounds, which are characterized by a generally higher stability towards oxygen and thus an easier handling as compared to alkyl phosphorus compounds, become available for use as catalysts or catalyst components in scCOz.
For example, compounds IV are perfluoroalkyl substituted, scC02-soluble analogues of triphenylphosphine (TPP), which is widely employed as a catalyst or catalyst component in organic solvents. Compounds V are analogues of the bidentate ligand 1,2-bis(diphenylphosphino)ethane (dppe), which is also often used.
scC02-soluble catalysts which consist of perfluoroalkyl substi-tuted aryl phosphorus compounds and a transition metal can be formed in situ from suitable metal-containing precursor com-plexes and the phosphorus compounds, or preformed complexes such as VIII-X can be used. Examples of possible transition metal components include Ni, Pd, Pt, Co, Rh, Ir, Fe, Ru, Os, Ti, W, Mo, and compounds of such metals. Examples of catalytic processes include hydrogenations, oxidations, C-C bond-forming reactions and polymerizations. The examples described in the following demonstrate the potential of these catalysts in scC02, without any limitation of possible applications being imposed thereby. In particular, the example of the hydroformy-lation demonstrates the critical positive influence of the perfluoroalkyl chain R1.
a) Chemoselective hydrogenation of polyenes to monoenes The chemoselective hydrogenation of polyenes to monoenes in scC02 in the presence of catalysts based on perfluoroalkyl substituted aryl phosphorus compounds is conveniently per-formed by heating a mixture of the substrate, HZ and compressed COZ in a high pressure reactor to a temperature above the critical point of the mixture. The chemoselective hydrogena-tion of polyenes in scCOz in the presence of perfluoroalkyl substituted phosphorus compounds can be performed at tempera-tures from 30 °C, preferably between 40 °C and 100 °C and at H2 partial pressures of between 1 and 100 bar, preferably between 1 and 50 bar. The total pressure ranges between 100 to 300 bar, preferably between 180 and 250 bar. The catalyst, for example, IXa/NEt3, is added to this mixture. The progress of the reaction can be followed by means of the decrease in pressure due to H2 consumption. When the reaction is performed in scC02, the tedious and solvent-intensive processing of the reaction mixture can be avoided; for example, the hydrocarbons are collected in a practically pure form by simple condensing in a cooling trap. Exemplified by the hydrogenation of iso-prene, it was shown that IXa in scCOz achieves selectivities for the formation of the monounsaturated products comparable to those of the related catalyst [ (PhzP (CHZ) 3PPh2}Rh (r~3-CeHll) ] in organic solvents (Table 4). The proportion of 3-methylbutene-1 is even somewhat higher in scCOz than in conventional solvents.
Table 4: Product ratios in the chemoselective hydrogenation of isoprene in organic solvents and in scC02.
2-methyl- 2-methyl- 2-methyl- 3-methyl-butane butene-1 butene-2 butene-1 reaction medium: 11.8% 20.8% 67.2% 0.1 DMSO/quinuclidine; T= 80 °C;
p(H2) = 6 bar; cat.: 0.5 mole [f PhzP(CH2)3PPh~}Rh(r~3-C8H")]
reaction medium: scCO~/NEt3; 10.3% 28.7% 53.8% 7.7%
T = 40 °C, p(H2) = 45 bar; cat.:
0.08 mole % IXa (Example 8) b) Hydroformylation of 1-octene The cobalt catalyzed hydroformylation in scCOz without the addition of a phosphorus component has been described in US
5,198,589. However, in common solvents, rhodium complexes with phosphorus ligands have many advantages over cobalt catalysts in hydroformylations and are therefore increasingly used in technology (B. Cornils, W.A. Herrmann (eds.), Applied Homoge-neous Catalysis with Organometallic Compounds, Vol. 1, VCH, 1996, p. 7f). However, the transfer of the catalyst system Rh/TPP, which is technically established in organic solvents, to the use in scC02 fails due to the insolubility of the active species in this medium. Until the supercritical state is reached, the reaction proceeds to a small extent due to the solubility of the catalyst in the olefin. At the critical point, the catalyst becomes insoluble; the supercritical phase consisting of the olefin and COZ is then colorless, and no further conversion of the olefin takes place (Example 10).
In contrast, with the perfluoroalkyl substituted TPP analogue IV, the rhodium-catalyzed hydroformylation of olefins proceeds smoothly in scCOz (Example )), the solubility of the catalyti-cally active species under these conditions being indicated by an intense yellow color of the supercritical phase. Under supercritical conditions, a conversion of 92% and an n/iso ratio of 4.6 is achieved in the hydroformylation of 1-octene to 1-nonanal and 2-nonanal using a Rh/IV catalyst. The corre-sponding values for the control experiment with unsubstituted TPP (Example 10) are 26% and 3.5, respectively. This example demonstrates the importance of the perfluoroalkyl chains to the use of the aryl phosphanes as catalysts or catalyst compo-nents in scCOz .
The hydroformylation of olefins in scC02 in the presence of catalysts containing perfluoroalkyl substituted phosphorus compounds is conveniently performed by heating a mixture of the catalyst, the olefin, CO, HZ and COZ in a high pressure reactor to a temperature above the critical point of the mixture. The rhodium-catalyzed hydroformylation of olefins in the presence of perfluoroalkyl substituted phosphorus com-pounds can be performed at temperatures from 30°C, preferably between 40°C and 100°C, and at CO and HZ partial pressures of between 1 and 120 bar, preferably between 1 and 60 bar. The total pressure ranges between 100 and 300 bar, preferably between 180 and 250 bar.
Example 1:
Preparation of 1-bromo-4-(1H,1H,2H,2H-perfluorooctyl)benzene (Ia) In a 500 ml three-necked flask equipped with a reflux con-denser, bubble counter and dropping funnel, 4.30 g (0.18 mol) of Mg turnings were added to 15 ml of Et20, and then 40.5 g (0.17 mol) of 1,4-dibromobenzene in 75 ml of EtzO was added dropwise. The resulting Grignard solution was stirred at room temperature for 3 d, the excess Mg was filtered off, and the content of the Grignard solution determined by titration (1.85 M, 94.9$).
To a solution of 43.8 g (92.5 mmol) of 1H,1H,2H,2H-perfluoro-octyl iodide and 2 spatula-full of [ (r~'-C8H12) CuCl] in 20 ml of THF was added dropwise 47.5 ml (87.9 mmol) of the previously prepared Grignard solution at 5°C. The color of the reaction mixture turned from yellow to brown, and a precipitate formed.
The mixture was diluted with 100 ml of THF and 100 ml of Et20 and heated to reflux for 4 h. After cooling, the reaction solution was hydrolyzed with 300 ml of saturated NH4C1 solu-tion. The blue aqueous phase was partitioned with 3 x 50 ml of Et20, and the combined organic phases were washed with 2 x 40 ml of H20 and dried over Na2S04. After removing the solvent, a light-brown, highly viscous raw product was ob-~
tained, which was fractionally distilled under oil pump vacuum through a Vigreux column (length: 19 cm, diameter: 16 mm). At a boiling temperature of 102-105 °C, 15.3 g of a colorless oil was collected, which contained 87.4 Ia according to a GC
analysis. An analytically pure sample could be obtained by preparative GC.
GC/mass m/z (~) 502 (55) [M'+] , 423 (15) [M'+- ('9Br) ] , 169 spectrum (EI) : (100) [M'+-CHZC6Fla]
elemental calc.: C: 33.42 H: 1.60 Br: 15.88 F: 49.09 analysis: found: C: 33.55 H: 1.70 Br: 15.97 F: 48.69 In an analogous way, compounds Ia-d as listed in Table 1 were prepared.
Example 2:
Preparation of di-(4-(1H,1H,2H,2H-perfluorooctyl)phenyl]-chlorophosphane (III) 8.77 g (17.4 mmol) of Ia was dissolved in 50 ml of Et20, and ml of n-BuLi (1.7 M in hexane) was slowly added dropwise to this solution at -50°C under an argon atmosphere whereupon the turbid solution became intensely yellow. Subsequently, the solution, which had warmed up to 0°C, was added dropwise to a solution of 1 . 51 g of C12PNEt2 ( 8 . 6 mmol ) in 20 ml of THF . The mixture was stirred in an ice bath at 0 °C over night, where-upon a precipitate formed. After filtration, the clear reac-tion solution was treated with gaseous HC1 with stirring at room temperature for about 30 minutes. After a few minutes already, a colorless precipitate formed, which was redissolved in the course of the reaction. For degassing the solution, it was freezed out in a nitrogen bath, evacuated by means of an oil pump, and rethawed under an argon atmosphere. In doing so, a precipitate again formed, which was filtered off. The fil-~
trate was concentrated under vacuum to about half its original volume and maintained at -20°C over night for crystallization.
Filtering, washing twice with Et20 and drying under high vacuum afforded 3.38 g of III as colorless crystals.
mass spectrum (EI) m/z (%) 912 (100) [M'+]
Example 3:
Preparation of tri-[3-(1H,1H,2H,2H-perfluorooctyl)phenyl]phos-phane (IV) To 3.85 g (6.88 mmol) of Ic in 10 ml of Et20 was added dropwise 4.1 ml of n-BuLi (1.7 M in hexane) in 10 ml of Et20 at -25°C
under an argon atmosphere within 35 minutes . The yellow solu-tion obtained was briefly warmed to 0°C, and then 284 mg (2.06 mmol) of PC13 in 10 ml of EtzO was added dropwise at -10°C within 20 min, whereupon a precipitate appeared. After min of stirring at room temperature, the reaction mixture was hydrolyzed with 20 ml of saturated NHQC1 solution. The aqueous phase was extracted with 3 x 20 ml of Et20, and the combined organic phases were first washed with 2 x 10 ml of H20 and then dried over Na2S04. Evaporating the solvent afforded a light-brown solid which was recrystallized from 10 ml of a THF/MeOH mixture to yield 1.50 g of a colorless solid, which contained 94.4% IV according to a GC analysis.
mass spectrum m/z (%) 1300 (100) [M"]
(EI) Example 4:
Preparation of 1,2-bis(di-~4-(1H,1H,2H,2H-perfluorooctyl)-phenyl~phosphino]ethane (Va) To 1.61 g (2.80 mmol) of Ia in 10 ml of Et20 was added dopwise 1.75 ml of n-BuLi (1.7 M in hexane) in 5 ml of Et20 at -35°C
under an argon atmosphere within 10 min. The yellow solution obtained was briefly warmed to 0°C, and then 0.15 g (0.67 mmol) of 1,2-bis(dichlorophosphino)ethane in 7 ml Et20 was added dropwise at -23°C within 25 min. After 10 min of stirring at room temperature, the reaction mixture was hydro-lyzed with 10 ml of saturated NHQC1 solution, the aqueous phase was extracted with 2 x 10 ml of EtzO, and the combined organic phases were dried over Na2S04. The solvent was removed, and recrystallization of the raw product from 2-3 ml of THF/MeOH
afforded 0.56 g of a colorless solid, which contained 93.1% Va according to a GC analysis.
mass m/z (%) 1782 (100) [M'+] , 1754 (15) [M'+-CHzCHz] , spectrum 1327 (30) [M'+- (P-C6H4-CHzCH2C6F13+H) ] , 1313 (10) (EI) : [M'+- (P-C6H4-CHzCHzC6F13+CH3) ] , 1300 (25) [M'+- (P-C6H4-CHzCH2C6F13+CzH4) ] , 877 (35) [M~+- (-CHZCHZ-P- (C6H4-CH2CHzC6F13) z) ]
elemental calc.: C: 39.08 H: 2.04 F: 55.41 P: 3.48 analysis: found: C: 39.04 H: 2.02 F: 55.28 P: 3.47 In an analogous way, compounds Va-d as listed in Table 1 were prepared.
Example 5:
Preparation of [(IV)3RhCl] (VIII) A solution of 520 mg (0.40 mmol) of IV in 3 ml of THF was added dropwise to a solution of 17 mg (0.02 mmol) of [((~z-C8H14) zRh (~,-C1 ~2] in 3 ml THF under an argon atmosphere within minutes, whereupon the previously orange-yellow colored solution turned dark red. It was stirred at room temperature for 30 min, and after removing the solvent, a dark-red solid remained which was recrystallized from 2 ml of a THF/MeOH
mixture. After drying the crystals under high vacuum, 156.0 mg of VIII was obtained as a dark-red solid.
Example 6:
Preparation of [(Ya)Rh(hfacac)] (IXa):
To a solution of 84.5 mg (0.20 mmol) of [ (r~4-C8H12) Rh(hfacac) ]
in 10 ml of THF was added dropwise 387 mg (0.20 mmol) of Va in 10 ml of THF at -78°C under an argon atmosphere. After comple-tion of the addition, the reaction solution was slowly warmed to room temperature, and after about 20 minutes of stirring at room temperature, a deep red-brown solution was obtained. The solvent was removed under oil pump vacuum, and the residual red-brown solid (0.52 g) was recrystallized from 5 ml of an MeOH/THF mixture. After 3 d of drying under high vacuum with slight heating, 0.31 g of the pure complex IXa was obtained.
mass spectrum m/z (~) 2092 (10) [M"]
(EI): (direct injection) elemental calc.: C: 36.16 H: 1.78 F: 52.65 P: 2.96 analysis: found: C: 36.03 H: 1.85 F: 52.53 P: 2.95 In an analogous way, compounds IXa-d as listed in Table 1 were prepared.
Example 7:
Preparation of trans- [ (Va) ZRuCl2] (X) To a suspension of 0.99 g of Ya (0.55 mmol) in 120 ml of ethanol was added a solution of 68.2 mg of RuCl3 hydrate (35-40% Ru, 0.23 mmol) in 4 ml of degassed water under an argon atmosphere. Subsequently, the mixture was heated to reflux for 2 h, whereupon the previously green colored suspension turned light yellow. After filtration, removing the solvent and drying under high vacuum, 0.74 g of X was obtained.
Example 8:
Chemoselective hydrogenation of isoprene in scC02 with IXa as a catalyst:
5.94 g of isoprene (87 mmol) was charged in a pressure reactor (V = 100 ml) flushed with Hz, and hydrogen was used to adjust a pressure of 45 bar (about 200 mmol) at room temperature. Then, 67 g of COZ was supplied to the autoclave by means of a com-pressor, upon which a total pressure of 135 bar resulted in the reactor. The reactor was then heated to +40. degree.C, the transi-tion of the mixture to the supercritical range being ensured by visual monitoring (inspection glass). A solution of 190 mg of the Rh complex IXa (0.09 mmol) in 2.3 g of NEt3 was then introduced in the pressure reactor by means of a sample injec-tion system, whereupon the previously colorless supercritical phase turned orange-yellow. After 19 h, the pressure was released, and the hydrocarbons were condensed in a cooling trap cooled with acetone/dry ice. The product distribution was established by GC.
. CA 02278572 1999-07-19 Example 9:
Hydroformylation of 1-octene in scCOz with [ (~4-C8H12)Rh(hfaCaC) ] /IV as a catalyst:
17.4 mg of [ (r~4-CeHl2)Rh(hfacac) ] (0.05 mmol) and 352 mg of IV
(0.27 mmol) were charged as solids to a pressure reactor (V =
20 ml) flushed with argon, and 1.50 ml of 1-octene (9.60 mmol) was added. Subsequently, a 1:1 CO/HZ mixture of gases was added at room temperature under a pressure of up to 60 bar. After about 20 minutes, 13.6 g of COz was supplied by means of a compressor. Then, the reaction mixture was heated to 60°C
which gave rise to a total pressure of 220 bar. The super-critical phase formed was homogeneous and had a yellow color.
Within the reaction time of 19 h, the internal pressure de-creased by about 25 bar to 190 bar. A 1H NMR spectroscopical analysis performed immediately after reaching the supercriti-cal state and 19 h later showed that a conversion of 92% to 1-nonanal (n-aldehyde) and 2-nonanal (iso-aldehyde) had been achieved in the supercritical medium with an n/iso ratio of 4.6.
Example 10:
Attempted hydroformylation of 1-octene in scCOz with [(r~4-CBH12)Rh(hfacac) ] /TPP as a catalyst:
19.1 mg of [ (r~'-CeHl2)Rh(hfacac) ] (0.05 mmol) and 72.5 mg (0.28 mmol) of TPP were charged as solids to a pressure reac-tor (V = 20 ml) flushed with argon, and 1.50 ml (9.6 mmol) of 1-octene was added. Part of the solids dissolved in the sub-strate to form a red-brown solution. Then, 60 bar of a 1:1 CO/HZ mixture of gases was added at room temperature, and then, about 20 minutes later, 13.6 g of COz was supplied by means of a compressor. After the reaction mixture had been heated to 60°C, an internal pressure of 225 bar resulted and did not _ CA 02278572 1999-07-19 change any more in the further course of the process. The supercritical phase formed was colorless, and an insoluble solid was present. A 1H NMR spectroscopical analysis performed with a sample taken immediately after reaching the supercriti-cal state (visual monitoring) showed that a conversion of 26%
to 1-nonanal (n-aldehyde) and 2-nonanal (iso-aldehyde) had been achieved with an n/iso ratio of 3.5. After 18 h in the supercritical state, the pressure was released, and the prod-ucts and educts were isolated. Another analysis by 1H NMR
showed that no more aldehyde had been formed in the super-critical state.
Example 11:
This Example shows the applicability of the present method to the use of aryl phosphates:
Preparation of tris[4-(1H,1H,2H,2H-perfluorooctyl)phenyl]
phosphate (XI):
The aryl phosphate XI was obtained by analogy with Examples (1) and (3) according to Scheme 3.
OMe OH
1. vf~. F~~O. rctl ~ p~>
\ ~ LIICH~hICF~~F, \ ~ tOIU~
Itr~.GHn)C"Ol lat.>. -20'C
1NF.0'C-> I3'C (~t)t~~2)6F
3. B6ry, CH~O~
-7a'C ..> 21'C
GC/mass m/z (%) 1348 (25) [M'+]
spectrum (EI) elemental calc.: C: 37.41 H: 1.79 P: 2.30 analysis: found: C: 37.29 H: 1.88 P: 2.23 31P NMR: 8 128.5 (CDC13) Scheme 3: Synthesis of aryl phosphate XI and selected analyti-cal data.
The aryl phosphate XI was employed in the hydroformylation of 1-octene (conditions: T = 65°C, p(HZ/CO) - 20 bar, 1-octene:
[Rh]:[P] - 2175:1:10) by analogy with Example 9. An analysis by NMR spectroscopy and gas chromatography of the reaction mixture revealed a conversion of 50% after 7.5 h and a conver-sion of 98% (n/iso = 5.6, determined by 1H NMR) after 88 h.
Example 12:
This Example shows the applicability of the present method when using the reaction mixtures in the hydrogenation of polar double bonds, especially in the enantioselective hydrogenation of amines. The control experiment demonstrates the positive influence of the perfluoroalkyl residues.
The perfluorinated chiral ligand (XIIb) and the unsubstituted parent compound (XIIa) were prepared by known methods (P. von Matt et al., Tetrahedron: Asymmetry 1994, 5, 573), compound III being used instead of Ph2PCl in the synthesis of XIIb. The iridium complexes [ (XII) Ir (cod) ] [BPh4] were employed for the enantioselective hydrogenation of Ph(CH3)C=NPh in scC02 under the conditions summarized in Scheme 4; XIIb proved superior to its parent compound XIIa with respect to both activity and selectivity.
)'h H H
1V H2 (30 bar)) T= 40°C H N-Ph Ph-N H
P CH3 scC02, d= 0.75 g/mL ph C~ h~C h cat.: [(XII)Ir(cod)][BPhe]
reacction time Yield of amine ee (R) (GC) (HPLC) X~2: R = H 20 h ~ ~ % ...
40 h 83% 60%
XQb: R = F(CFp)s(CI-!2)2 20 h 96% fib°/.
Scheme 4: Use of perfluorinated ligands for the enantioselec-tive hydrogenation of imines in scC02.
Example 13:
This Example shows the applicability of the present method when using the reaction mixtures in C-C bond-forming reac-tions, especially in the polymerization of phenylacetylene.
Due to its non-linear optical and magnetic properties, polyphenylacetylene is an important polymeric material in materials technology (G. Costa, in: Comprehensive Polymer Science, Vol. 4, G. Allen, J.C. Bevington (eds.), Pergamon Press, Oxford, 1989, p. 155ff).
Under an Ar atmosphere (glove box), 7.0 mg (2.36 x 10-z mmol) of [ (r~4-C,HB) Rh (acac) ] (acac - acetylacetonate) was weighed together with 30 mg (2 . 31 x 10-z mmol) of [4-F (CF2) 6 (CH2) zC6H4] sP
(synthesis by analogy with that of IV) in a stainless steel high pressure reactor (V = 27 ml) equipped with an inspection glass, PTFE stirring bar, bores for temperature sensors, isolating valve and ball valve, and about 10 equivalents of NEt3 was added. A metering device with a gas tank was mounted to the ball valve of the autoclave by a Swagelok screw j oint and filled with 0.25 ml (2.27 mmol) of phenylacetylene.
Through the needle valve, COZ (20.9 g, d = 0.78 g~ml-1, 83 bar) was filled in the reactor by means of a compressor, and the reaction mixture was heated to 40-42°C with stirring, where-upon the pressure increased to 130-135 bar, and a homogeneous yellow phase was formed. The gas tank was filled with 150-180 bar of argon, the metering device was pressurized, the monomer was injected by opening the ball valve towards the reactor volume, and the metering device was repeatedly flushed with argon pressure. A spontaneous change in color to orange was observed, and after a few seconds already, an orange precipitate was deposited at the inspection glass of the autoclave. After two hours of stirring, the reactor was cooled to 0°C, and the pressure released, and then 20 ml of THF and 1 ml of glacial acetic acid were added under an argon atmos-phere, and the mixture was stirred over night. With vigorous stirring, the red solution was siphoned into a two-necked flask with 200 ml of MeOH for precipitation of the polypheny-lacetylene, and solid residues were isolated separately. After filtration and washing with MeOH and acetone, the product fractions were dried under oil pump vacuum.
overall yield: 213 mg (2.09 mmol, 92~), orange platelets (cis-transoidal) + red crystals (cis-cisoidal) in a weight ratio of 40:60 1H NMR, CDC13 8 6.93-6.91 (m, 3H, meta/para), 6.65-6.61 200.1 l~iz (m, 2H, ortho) , 5.82 (s, 1H, vinyl) (soluble fraction, 6~ie ~ 77-78~.
cis-transoidal PPA) Example 14:
This experiment shows the possibility of separating the cata-lyst from the product, exemplified by the hydroformylation of 1-octene.
14.4 mg (0.034 mmol) of [ (r~4-C8H12)Rh(hfacac) ] , 337 mg (0 .260 mmol) of [4-F (CFZ) 6 (CHz) zC6H4] 3P (synthesis by analogy with IV) and 10.8 g (96 mmol) of 1-octene were separately charged in a 275 ml autoclave with an inspection glass. After sealing the reactor, 20 bar of synthesis gas was added, and sufficiently CO2 was added by means of a compressor to give a total pressure of 120 bar at room temperature. Then, the mixture was heated to 65°C with stirring. A homogeneous yellow phase formed, and an internal pressure of about 210 bar re-sulted. After 24 h, an internal pressure of 190 bar was read.
The mixture was cooled down to room temperature to form a two-phase system consisting of a colorless gaseous phase and a yellow liquid phase.
After another 24 h, COZ was removed by carefully releasing the pressure through a valve provided at the reactor head, until the volumes of the liquid and gaseous phases present in the reactor were approximately equal. Then, after closing the valve, the mixture was heated to 60°C. During this, the volume of the liquid phase decreased, and an internal pressure of 100 bar was reached. Then, a constant amount (about 10 1/min) of the upper phase was removed through the top valve and passed through a separator. In order to keep the pressure within the reactor constant, COZ was constantly added through a valve provided at the bottom of the reactor. After about 15 minutes, 4 ml of a colorless liquid had gathered in the sepa-rator. An analysis by 1H NMR showed that 95% of the mixture consisted of 1-nonanal and 2-nonanal (n/iso = 2.5). By atom absorption spectroscopy (AAS), a Rh content of 9 ppm was determined in the separated mixture of aldehydes.
Claims (19)
1. Reaction mixtures, essentially consisting of reactants, a catalyst and carbon dioxide in a supercritical state (scCO2), characterized in that said catalyst or components thereof are phosphorus compounds containing perfluoroalkyl substituents of general formula R1 [R1= -(CH2)x(CF2)y E
(E = F, H, x = 0 - 4 , y = 2 - 12)].
(E = F, H, x = 0 - 4 , y = 2 - 12)].
2. The reaction mixtures according to claim 1, characterized in that said phosphorus compounds contain one or more aryl residues to which one or more perfluoroalkyl chains of general formula R1 are attached.
3. The reaction mixtures according to claim 1 or 2, characterized in that said catalyst contains one or more transition metal atoms.
4. The reaction mixtures according to claim 3, characterized in that rhodium or ruthenium or iridium is employed as said transition metal.
5. A process of performing catalytic reactions, characterized in that the reactions are performed in a reaction mixture according to claims 1 to 4.
6. The process according to claim 5, characterized in that said catalytic reaction is a hydrogenation.
7. The process according to claim 6, characterized in that said hydrogenation is a chemoselective hydrogenation of polyenes to monoenes.
8. The process according to claim 7, wherein isoprene is used as said polyene.
9. The process according to claim 6, characterized in that said reaction is the hydrogenation of a polar double bond.
10. The process according to claim 9, characterized in that said polar double bond is a C=N double bond.
11. The process according to claim 5, characterized in that said catalytic reaction is a hydroformylation of olefins or mixtures of olefins.
12. The process according to claim 11, wherein olefins having a chain length of C4-C20 are used.
13. The process according to claim 12, wherein 1-octene is used as said olefin.
14. The process according to claim 5, characterized in that said reaction is a C-C bond-forming reaction.
15. The process according to claim 14, characterized in that said reaction is a polymerization reaction.
16. The process according to claim 15, characterized in that the monomer of said polymerization is an acetylene derivative.
17. The process according to claim 5, characterized in that the product and the catalyst are separated using the extractive properties of scCO2, the catalyst being recovered in an active form.
18. The process according to claim 17, characterized in that the density of the supercritical reaction medium is adjusted by a variation of the pressure and/or temperature to achieve extraction of the product from the reaction mixture.
19. The process according to claim 17, characterized in that the density of the supercritical reaction medium is adjusted by a variation of the pressure and/or temperature to achieve extraction of the catalyst from the product and reaction mixture.
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DE19702025.9 | 1997-01-23 | ||
DE19702025A DE19702025A1 (en) | 1997-01-23 | 1997-01-23 | Use of perfluoroalkyl-substituted phosphorus compounds as ligands for homogeneous catalysis in supercritical carbon dioxide |
PCT/EP1997/007266 WO1998032533A1 (en) | 1997-01-23 | 1997-12-23 | Use of perfluoroalkyl substituted phosphorus compounds as ligands for homogeneous catalysis in supercritical carbon dioxide |
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JP (1) | JP2001526582A (en) |
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CA (1) | CA2278572A1 (en) |
DE (2) | DE19702025A1 (en) |
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Cited By (2)
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US8222415B2 (en) | 2006-10-03 | 2012-07-17 | Johnson Matthey Public Limited Company | Chiral phosphorus compound |
CN109312014A (en) * | 2016-05-27 | 2019-02-05 | Sk新技术株式会社 | Oligomerisation catalyst and the method for preparing ethylene low polymer using it |
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DE69912097T2 (en) * | 1998-01-28 | 2004-07-01 | Cambridge University Technical Services Ltd. | USE OF COMPRESSED CARBON DIOXIDE IN CHEMICAL REACTIONS |
AU6231699A (en) | 1998-09-30 | 2000-04-17 | Atofina Vlissingen B.V. | Fluorous phosphines and processes for their preparation |
DE19853748A1 (en) | 1998-11-21 | 2000-05-25 | Studiengesellschaft Kohle Mbh | Production of chiral aldehyde by enantioselective hydroformylation, useful e.g. as intermediate for pharmaceuticals, uses transition metal catalyst complex containing phosphine-phosphite ligand |
AU1574400A (en) * | 1998-12-04 | 2000-06-26 | University Court Of The University Of St Andrews, The | Alkene hydroformylation catalyst |
FR2789391B1 (en) * | 1999-02-10 | 2003-06-27 | Atochem Elf Sa | PROCESS FOR THE PREPARATION OF TRIS ((1H, 1H, 2H, 2H-PERFLUOROALKYL) ARYL) PHOSPHITES, THE SAID FLUORINATED ARYLPHOSPHITES AND THEIR APPLICATIONS IN BIPHASIC FLUORINATED CATALYSIS |
US6747179B1 (en) | 1999-08-20 | 2004-06-08 | North Carolina State University | Carbon dioxide-soluble polymers and swellable polymers for carbon dioxide applications |
WO2001014289A2 (en) * | 1999-08-20 | 2001-03-01 | North Carolina State University | Polymer-bound catalysts for use in carbon dioxide |
DE10123467A1 (en) * | 2001-05-15 | 2002-11-21 | Studiengesellschaft Kohle Mbh | Activation of cationic transition metal catalyst, useful in e.g. metathesis, oligomerization reaction, involves using ionic liquid and compressed carbon dioxide |
EP1452549B1 (en) | 2001-10-16 | 2010-11-17 | Sekisui Chemical Co., Ltd. | Process for producing modified polymer, apparatus for producing modified polymer, and modified polymer |
WO2013068389A1 (en) * | 2011-11-10 | 2013-05-16 | Basf Se | Process for the preparation of formic acid by reaction of carbon dioxide with hydrogen |
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GB2074040B (en) * | 1980-04-22 | 1984-05-10 | Air Prod & Chem | Catalysts for the synthesis of hydrogen peroxide |
DE3563611D1 (en) * | 1984-03-06 | 1988-08-11 | Mitsubishi Chem Ind | Method for the partial hydrogenation of conjugated dienes |
DE59205529D1 (en) * | 1991-01-25 | 1996-04-11 | Ciba Geigy Ag | Diphosphines containing silane groups, immobilized diophoshins and their use as hydrogenation catalysts |
US5171907A (en) * | 1991-07-01 | 1992-12-15 | Phillips Petroleum Company | Preparation of hydrogenation catalyst and hydrogenation process therewith |
US5198589A (en) * | 1992-04-28 | 1993-03-30 | The United States Of America As Represented By The United States Department Of Energy | Cobalt carbonyl catalyzed olefin hydroformylation in supercritical carbon dioxide |
DE69425917T2 (en) * | 1993-03-12 | 2001-01-18 | Takasago Perfumery Co Ltd | Methods of making optically active aldehydes using transition metal-phosphine complexes, and methods of making an intermediate in the manufacture of carbapenem antibiotics using these complexes |
JPH06263681A (en) * | 1993-03-12 | 1994-09-20 | Mitsubishi Gas Chem Co Inc | Production of optically active aldehyde |
DE4333307A1 (en) * | 1993-09-30 | 1995-04-06 | Hoechst Ag | Cyclic compounds of trivalent phosphorus |
EP0646590B1 (en) * | 1993-10-01 | 1999-08-25 | Novartis AG | Ferrocenyldiphosphines substituted with fluoroalkyl groups as ligands for homogeneous catalysts |
US5523437A (en) * | 1993-10-07 | 1996-06-04 | Sumitomo Chemical Co., Ltd. | Tertiary phosphine compound and transition metal complex comprising the same as ligand |
US5639910A (en) * | 1993-11-04 | 1997-06-17 | Research Development Corporation Of Japan | Method for producing formic acid or its derivatives |
US5567856A (en) * | 1995-05-30 | 1996-10-22 | Hoechst Celanese Corporation | Synthesis of and hydroformylation with fluoro-substituted bidentate phosphine ligands |
-
1997
- 1997-01-23 DE DE19702025A patent/DE19702025A1/en not_active Withdrawn
- 1997-12-23 WO PCT/EP1997/007266 patent/WO1998032533A1/en active IP Right Grant
- 1997-12-23 EP EP97954464A patent/EP0959987B1/en not_active Expired - Lifetime
- 1997-12-23 DK DK97954464T patent/DK0959987T3/en active
- 1997-12-23 AT AT97954464T patent/ATE203934T1/en not_active IP Right Cessation
- 1997-12-23 JP JP53152098A patent/JP2001526582A/en active Pending
- 1997-12-23 ES ES97954464T patent/ES2159158T3/en not_active Expired - Lifetime
- 1997-12-23 CA CA002278572A patent/CA2278572A1/en not_active Abandoned
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Cited By (5)
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US8222415B2 (en) | 2006-10-03 | 2012-07-17 | Johnson Matthey Public Limited Company | Chiral phosphorus compound |
US8404843B2 (en) | 2006-10-03 | 2013-03-26 | Johnson Matthey Public Limited Company | Chiral phosphorus compound |
US8735583B2 (en) | 2006-10-03 | 2014-05-27 | Johnson Matthey Public Limited Co. | Chiral phosphorus compound |
CN109312014A (en) * | 2016-05-27 | 2019-02-05 | Sk新技术株式会社 | Oligomerisation catalyst and the method for preparing ethylene low polymer using it |
US11235315B2 (en) * | 2016-05-27 | 2022-02-01 | Sk Innovation Co., Ltd. | Oligomerization catalyst and method for preparing ethylene oligomer using same |
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DK0959987T3 (en) | 2001-10-22 |
ATE203934T1 (en) | 2001-08-15 |
EP0959987A1 (en) | 1999-12-01 |
EP0959987B1 (en) | 2001-08-08 |
ES2159158T3 (en) | 2001-09-16 |
DE59704265D1 (en) | 2001-09-13 |
JP2001526582A (en) | 2001-12-18 |
WO1998032533A1 (en) | 1998-07-30 |
DE19702025A1 (en) | 1998-07-30 |
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