TW528759B - Diphosphines containing a 2-phospha-tricyclo [3.3.1.1.{3,7}] decyl group - Google Patents
Diphosphines containing a 2-phospha-tricyclo [3.3.1.1.{3,7}] decyl group Download PDFInfo
- Publication number
- TW528759B TW528759B TW087105264A TW87105264A TW528759B TW 528759 B TW528759 B TW 528759B TW 087105264 A TW087105264 A TW 087105264A TW 87105264 A TW87105264 A TW 87105264A TW 528759 B TW528759 B TW 528759B
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- Prior art keywords
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- patent application
- group
- decyl
- phosphorus
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- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 title claims description 11
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 150000001768 cations Chemical class 0.000 claims abstract description 21
- 230000006315 carbonylation Effects 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 11
- 125000004429 atom Chemical group 0.000 claims abstract description 10
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 5
- 230000000737 periodic effect Effects 0.000 claims abstract description 3
- 125000004437 phosphorous atom Chemical group 0.000 claims abstract description 3
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims abstract 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 12
- 229940122361 Bisphosphonate Drugs 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- 150000004663 bisphosphonates Chemical class 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 239000001294 propane Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 238000012937 correction Methods 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 239000013589 supplement Substances 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 239000012771 household material Substances 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 229910052763 palladium Inorganic materials 0.000 claims 1
- 229910052697 platinum Inorganic materials 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- -1 2-phospha-tricyclo[3.3.1.1{3,7}]decyl group Chemical group 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- 150000001450 anions Chemical class 0.000 description 12
- 239000002253 acid Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 4
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 229940017219 methyl propionate Drugs 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000004702 methyl esters Chemical class 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000002079 cooperative effect Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- REPVLJRCJUVQFA-UHFFFAOYSA-N (-)-isopinocampheol Natural products C1C(O)C(C)C2C(C)(C)C1C2 REPVLJRCJUVQFA-UHFFFAOYSA-N 0.000 description 1
- UIRWNAVHKJFQQG-UHFFFAOYSA-N 1,1,1,3,3,5,5,5-octafluoropentane-2,4-dione Chemical compound FC(F)(F)C(=O)C(F)(F)C(=O)C(F)(F)F UIRWNAVHKJFQQG-UHFFFAOYSA-N 0.000 description 1
- HMCUNLUHTBHKTB-UHFFFAOYSA-N 1,4-dimethoxybutane Chemical compound COCCCCOC HMCUNLUHTBHKTB-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- SYLMLKKURPTCSO-UHFFFAOYSA-N 1-phosphanylethylphosphane Chemical compound CC(P)P SYLMLKKURPTCSO-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- PXNSSVGVEXKKHS-UHFFFAOYSA-N 18,18-dimethylnonadecanoic acid Chemical compound CC(C)(C)CCCCCCCCCCCCCCCCC(O)=O PXNSSVGVEXKKHS-UHFFFAOYSA-N 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- LXFQSRIDYRFTJW-UHFFFAOYSA-N 2,4,6-trimethylbenzenesulfonic acid Chemical compound CC1=CC(C)=C(S(O)(=O)=O)C(C)=C1 LXFQSRIDYRFTJW-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- OQLZINXFSUDMHM-UHFFFAOYSA-N Acetamidine Chemical compound CC(N)=N OQLZINXFSUDMHM-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- AYIGKSDUXHSUID-UHFFFAOYSA-N CCC.C(C)(C)(C)PC(C)(C)C.C(C)(C)(C)PC(C)(C)C Chemical compound CCC.C(C)(C)(C)PC(C)(C)C.C(C)(C)(C)PC(C)(C)C AYIGKSDUXHSUID-UHFFFAOYSA-N 0.000 description 1
- 229910006111 GeCl2 Inorganic materials 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- LCTONWCANYUPML-UHFFFAOYSA-M Pyruvate Chemical compound CC(=O)C([O-])=O LCTONWCANYUPML-UHFFFAOYSA-M 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 208000002903 Thalassemia Diseases 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- YBCVMFKXIKNREZ-UHFFFAOYSA-N acoh acetic acid Chemical compound CC(O)=O.CC(O)=O YBCVMFKXIKNREZ-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- NRCHMAQSQFBYHE-UHFFFAOYSA-N azane;pyridine Chemical compound N.N.C1=CC=NC=C1 NRCHMAQSQFBYHE-UHFFFAOYSA-N 0.000 description 1
- 229940116229 borneol Drugs 0.000 description 1
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- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
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- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
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- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
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- 239000003085 diluting agent Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- VXHUBGOVNPJIEI-UHFFFAOYSA-N ethyl acetate;propanoic acid Chemical compound CCC(O)=O.CCOC(C)=O VXHUBGOVNPJIEI-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- 238000001030 gas--liquid chromatography Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- QHGIKMVOLGCZIP-UHFFFAOYSA-N germanium dichloride Chemical compound Cl[Ge]Cl QHGIKMVOLGCZIP-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
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- 150000002576 ketones Chemical class 0.000 description 1
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- 239000000314 lubricant Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- KJALUUCEMMPKAC-ONEGZZNKSA-N methyl (e)-pent-3-enoate Chemical compound COC(=O)C\C=C\C KJALUUCEMMPKAC-ONEGZZNKSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N methyl acetate Chemical compound COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- XJMOSONTPMZWPB-UHFFFAOYSA-M propidium iodide Chemical compound [I-].[I-].C12=CC(N)=CC=C2C2=CC=C(N)C=C2[N+](CCC[N+](C)(CC)CC)=C1C1=CC=CC=C1 XJMOSONTPMZWPB-UHFFFAOYSA-M 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
- B01J31/2461—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as ring members in the condensed ring system or in a further ring
- B01J31/248—Bridged ring systems, e.g. 9-phosphabicyclononane
- B01J31/2485—Tricyclic systems, e.g. phosphaadamantanes and hetero analogues
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
- C07F9/65683—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
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- B01J2531/82—Metals of the platinum group
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/828—Platinum
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Description
528759 A7 B7 五、發明説明(1 ) 發明說明 本發明係有關新穎之二膦化物、新穎之羰基化催化劑與 經由在含新穎羰基化催化劑中,其與一氧化碳和共同1應 物反應之不飽和化合物之羰基化作用之方法。 談基化反應在此技藝中為習知的。例如歐洲專利-A — 0,495,547揭示數傭例子,其中端賴於共同反應物之特性而 將晞烴轉化成硫酯、酸、酐、與醯胺等。其它在製造醛; 酮;羧酸;酯;醯胺和其它羧酸衍生物;内酯;内醯胺和 有關之N-雜環與背景文獻之例子可在莫斯(Messrs)HM可 古汗(Colquhoun)、DJ湯普森(丁^叫⑽幻與Mv端格 (Twlgg)(1991年普雷南(Pienum)出版)所著,,羰基化作用,,中 發現。一般反應速率級數為每莫耳催化劑(根據金屬計算) 每小時至高數百莫耳產物。内不飽和時,反應速率甚至較 數級為低。亦即為需相當大量之催化劑或延長反應時間。 本發明者設計提供較有活性之羰基化催化劑。令人驚訝 地,咸發現有高活性之羰基化催化劑可經組合以下而得…/ (1)由元素週期表選擇之8、9或10族金屬陽離子,和 (i i)下式之二膦化物 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) R1>p-r2-pr3r4 其中R2代表共價橋基,…代表與磷原子一起之二價基, 錢結視需要之經取代2_磷-三環[3.3.1.1(3,7}]癸基^其 衍生物,而其中一或多個碳原子經雜原子取代,且其中r、3 和R4分別代表至高20個原子之單價基或結合成至高π 個原子之雙價基;咸信可用在製備羰基化催化劑之二騰-化 -4 - 本纸張尺度適财_家^T^NS) 528759 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明(2 ) 物亦為新穎的。 化合物二環[3.3.1·1{3,7}]癸烷為學名,而較俗知為金剛 烷。因此,視需要之經取代2_磷-三環[3 3」uw]癸基 在本專利說明書將示為,,2_ΡΑ”基(如2_磷金剛基)。 較佳為2 -ΡΑ基在1,3,5或7之位置的一或多個經至高 為20個原子之單價基及5取代。R;之典型例包括甲基、三 氟甲基、乙氧基、苯基、與4_十二烷基苯基。更佳為2_ PA基在1,3,5和7每一位置經適當之相同基取代。 2 - p A基骨架上較佳為添加雜原子而非2 _磷原子。適當 之♦原子為氧和硫原子。此些雜原子適於在6,9和1 〇之 位置。 取佳足二價基為2-磷-1,3,5,7 -四甲基-6,9, 10 -三噚金 剛基。 單價基R3和R4每一者可各自選自(經取代)烴基,就如 甲基、苯基、吡啶基、或〇,〇 -二(第三-丁氧基)苯基、與 (經取代)雜烴基,就如三甲基矽烷基或烷氧基。或者r3和 了 起形成雙價基,如I,6·己婦、I,3或1,4_環辛歸· 等等較佳為R3和R4 —起形成2-PA基,最佳為同於R1 之雙價基。 用在本發明羰基化催化劑之較佳配位基為1,2 - P,P,-二 (2_%-1,3,5,7-四甲基-6,9,10-三氧三環-[3.3.1.1{3,7}癸 基)乙燒(DPA2) ; 1,3彳,?,-二(2-磷-1,3,5,7-四甲基- 6,9,1〇-三氧三環[3311{37}癸基)丙烷(〇1^3); 1,2- 1",1)、二-全氟基(2-磷-1,3,5,7-四甲基-6,9,10-三氧三環 -5- 本紙張尺度適用中國國家標準(⑽)爾格(21〇乂 297公楚) (請先閲讀背面之注意事項再填寫本頁)
528759 經濟部中央標準局員工消費合作社印製 Α7 Β7 五、發明説明(3 ) [3.3.1·1{3,7}-癸基)乙烷,1,3-Ρ,Ρ·-二-全氟基(2-磷-1,3,5,7-四甲基-6,9,10-三氧三環[3311{3,7}癸基)丙 烷,1,2-Ρ,Ρ’ -二-(2 -磷-1,3,5,7·四(三氟甲基)-6,9,10- 二氧二環[3.3·1·1{3,7}癸基)乙垸與 1,3-?,?,_二_(2 -磷-1,3,),7-四(三氟甲基)-659,1〇_三氧三環[3311{37}癸 基)丙烷,而最佳為DP A3。 製備所足義之配位基可以類似於喬安(J〇anne)H道寧 (D〇Wning)小姐所著"一些新穎機能之第二和第三膦之珍貴 金屬錯合物 ’’(PRECIOUS METAL COMPLEXES 〇F SOME NOVEL FUNCTIONALISED SECONDARY AND TERTIARY PHOSPHINES)之第三章所揭示製備第二膦13,5,7四甲基 ^,々一-三吟^-磷-金剛烷之方法丨在^^年^月提至布 里斯托(Bristol)大學之論文)。例如製備〇ρα3是將2,4-戊 二酮加至1,3 -二磷醯丙烷中。製備不對稱配位基可用例如 含有第三磷醯基和第一磷醯基之二膦化物。或者其可經由 偶合第二2-磷-三環[3.3.1.1{3,7}]癸烷與另一第二單膦化 物或其它此技藝中已知法製備。製造經取代配位基可以例 如使用經取代2,4 -戊二酮例如全氟基_ 2,4 -戊二酮或 1,1,1,5,5,5 -六氟基_2,4_戊二酮與膦化物反應。 根據現今IUPAC符號,8,9和1〇族金屬陽離子各為 Fe、Ru、〇s; Co、Rh、II^T7Ni、Pd、*Pt。% 同在”羰基化作用π中所述,每一陽離子可用在不同之羰基 化反應。 咸發現9族金屬陽離手和丨〇族金屬陽離子(在較舊文獻 -6- 本紙張尺度適用中國國家標準(CNS ) Α4規格(210Χ297公釐) (請先閲讀背面之注意事項再填寫本頁) 、言 528759 經濟部中央標準局員工消費合作社印製 A7 B7 _五、發明説明(4 ) 中為鉑族金屬陽離子)在用於本發明新穎催化劑中會有特別 佳之結果。 適合之金屬陽離子之來源可在”羧基化作用,,中找到而對 熟諳此技藝者將不構成問題。同樣地,製備催化劑系(實際 為前驅物,就地形成之活性物可能稍不同於此中所揭示之 前驅物)是循著由J Η道寧小姐論述中所揭示之一般法。 可用在不同羰基化反應之催化劑系在歐洲專利_ A _ 0,495,547和幾基作用π中描述。當應用在不飽和化合 物’特別是乙晞系不飽和化合物之加成羰基化作用,其在 有關反應速度上特別卓越。(在此顯示針對α -烯·烴之)後段 反應係依下列反應進行: RCH二CH2+C〇+HY-> RCH2CH2C〇Y ; Y=H,〇H,〇R,NR2 等等 内烯烴之加成羰基化作用為類似的。然因其高度之異構 化活性,一般產物類似於有相對應α烯烴反應者。 亦即催化劑系可用在,,加氫醛化反應”、”加氫羧化反應 加氫酯化反應"、"加氫醯胺化反應,,等等。 當然,此種羰基化反應可用共同反應物、溶劑等等。此 外,可用不同之陰離子以當為金屬陽離子之相對離子。其 例包括陰離子,其為具pKa(在18。〇水中測量)小於6 ,較 佳為小於4之酸的共軛鹼。由此些酸衍生之陰離子與金屬 陽離子沒有或僅有微弱之配位,亦即陰離子與陽離子間有 少許或無共價之交互作用。以此些陰離子為基礎之催化劑 顯示良好之活性。 適合之陰離子包括由布忍斯特(Br〇nsted)酸所衍生之陰離 本纸張尺度適用中國國家標準(CNS )A4ii^7x 297^t) C請先閲讀背面之注意事項再填寫本頁) 衣· 訂 528759
經濟部中央標準局員工消費合作社印製 :t由磷酸和硫酸且特別是由磺酸與(南化)羧酸,如三 氟酷酸=2,6_二-氯基苯甲酸、與2,6-雙(三說甲基)笨甲 酸或二氟醋酸等等。特別佳為由磺酸衍生之陰離子,例如 甲〜酸二氟甲磺酸、第三-丁磺酸、對-甲苯磺酸和 2,4,6-三甲基苯磺酸。 、 此外,錯合陰離子亦適合,如組合路易士酸、如Bp] B(C6F5)3’ Aici3, SnF2, Sii(CF3S〇3)2, 311(:12或 GeCl2,與質 子fe,較佳為pKa小於5 ,如磺酸,例如CFsS〇3H或 CI^S〇3H或氫鹵酸,如HF或HC1,或組合路易士酸與醇 所製成< 陰離子。此種鳝合物陰離子之範例為BF4_,SnC^_ [SnCl2· CF3S〇3]·和 pf6-。 3 : 羰基化反應在中等溫度下合宜地進行。因此,此方法適 宜在3〇至200 °C,較佳為5〇至刚。C之溫度範圍進行。 反應壓力亦極大地不同、例如,反應可在壓力為i至2⑻ 巴之計示壓力,較佳為5至60巴之計示壓力下進行。 所供以足一氧化碳較佳為莫耳量超過不飽和化合物和共 同反應物"Y Η ’’。此外,所使用之不飽和化合物和共同反 應物適於在莫耳比例在.1 0 ·· i至i ·· i 〇,較佳為5 : 1 至1 · 5 ’更佳為2 : 1至1 : 2之範圍。 催化劑系所使用之量並非絕對而可在極大範圍内改變。 通^使用量為每莫耳不餘和化合物有1〇_8至1〇-1,較佳為 至1 0-2莫耳金屬原子。 製備本發明催化劑系一般使用配位基之量略超過金屬陽 離子(量,示以每莫耳原子之陽離子中之莫耳配位基。一 * -8- 本纸張尺度適用中國國家標準(CNS ) Α4規格(210X297公羞) (請先閎讀背面之注意事項再填寫本頁)
528759
、發明説明( 6 經濟部中央標準局員工消費合作社印製 般遠擇配位基之量為每莫耳原子之陽離子有0.5至10莫耳 心羔而,咸信·較佳之催化劑系之活性類是根據每莫 、=離子有等莫耳量之雙配位基。因A,每莫耳陽離子中 Γ又配位基之莫耳量較佳為1至3,更佳為i i 2。含有 古、較佳為使用稍大之量。陰離子之量為每莫耳陽離子 〇’5至15,較佳為1至8莫耳。 、本^發明法中,起始物質與所形成之羰基化產物可當為反 應稀釋劑。因此,不需使用分離溶劑。然而,羰基化反應 可在另含溶射而㈣進行。在此情料,建議使用㈣ 烴,如石蠟和異烷烴,甚至是醚,就像2,5,三呤烷(二 醇一甲醚),一乙酸和苯甲醚;颯就如p塞吩燒,和芳香 烴就如甲苯。 =飽和化合物可有一或多個不飽和鍵且較佳為每分子含 2至30個碳原子之烯烴。不飽和键可在内部或末端,催化 劑特別利於轉化内婦烴。特別佳為每分子含2至22個碳原 子之烯烴,如乙晞、丙烯、^或八丁缔、^或内己婦、i或内辛烯、二異丁烯、三異丁晞、三丙烯、内癸烯、内 c14晞烴、與内c15-C18烯烴。 不飽和化合物中,一或多個氫原子可經其它原子取代, 如鹵素原子或原子基團,如經基、氰基,如甲氧基或乙氧 基或胺基,如二甲基··和二乙基-胺基。 另外較佳之不飽和化合物種類為由幾酸之不飽和酯與不 飽和羧酸酯所組成。例如起始物質可為羧酸如醋酸或丙酸 之乙晞基酯’或其可為不飽和酸之燒基酯,如丙缔酸或異 -9 本紙張尺度適用中國國家標準(CNS ) A4規格(.210X297公楚) (請先閲讀背面之注意事項再填寫本頁) if. » 17 7 528759 五、發明説明( 丁婦之甲基或乙基酉旨。 另外較佳之不飽和化八 ^ ^ "物種類由環二烯烴組成,其通常 不月匕叛基化。例如,起始物 吊 烯以違4 - π 物^ Τ為二環戊二婦或原冰片二 締以產生一酯、二醯胺岑-々 為單體。 次一I寺寺,其可在聚合反應中用 在本發明之加成幾基仆女、 %4、以、 匕万法中足適合共同反應物包括各 親核性邵份和流動氫原子之化合物。 口 較:圭::核性化合物包括分子氫、水和醇,例如單羥 醢,乙醇,異丙醇和卜丁醇,和多元醇,如乙二 醇’ 1,4 · 丁二醇和甘、击·贫結· 、 _ '' ,一級或二級(多)胺或醯 畔 胺,N,N-二甲基乙二胺;芳香醇和羧酸,如 •曰酉义’二甲基醋酸和丙酸。較佳為分子氫、每分子各卜 6個碳原子之單羥醇和每分子含2至6個碳原子: 醇。 了工 物特=為1_丁醇、甲醇和丨,4-丁二醇。當為共同反應 :物的用途為生產有價值之幾基化產物,如丙酸甲 酉曰丙鲅丁 和1,4 -二醯氧基丁烷。此些化合物有商業上 I用途且可當為溶劑與調味組成物與香水。 另外較佳之共同反應物為烷基酚類,其中一或多個烷基 之土南j〇,典型為6至22個碳原子連於紛分子上。與此 些共同反應物之加成羰基化作用產生烷基苯基酯,其當 為工業用途之合成潤滑劑,但是特別是用在馬達引擎上。 現在,將用以下範例更進一步描述本發明,但並非限定 其範圍。除非另有所指,否則所有實驗均在磁攪摔之 -10- M氏張尺度適用中國國家標準(CNS ) A4規格(2I〇x29:7公釐) (請先閲讀背面之注意事項再填寫本頁)
、1T 經濟部中央樣準局員工消費合作社印製 528759 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明(9 封住反應器。加熱教壓器φ 一丄 。 、 …、全咨中又成份至90 °C並維持此溫0.25 小時。冷卻後,由孰壓器成 …成份中取出樣品並以氣液層析術 分析。 乙婦在8000莫耳每|> 斗母旲耳Pd每小時(莫耳/莫耳.小時)之 平均速率以1 〇〇%選擇性弇冬 平几王轉化成丙酸甲酯。 例3 重覆例2 ,但是利用1 〇臺 毛升水和40毫升二乙二醇二甲 酸當為反應物/溶劑且方法φ + 、 万凌中又溫度為110 t;。在2小時後 冷却熱壓:器。 · 乙婦在1500莫耳/莫耳小 、 4呼 < 千均速率以100%選擇性 完全轉化成丙酸。 例4 重覆例2,然而使用3 〇亳弁 升丙烯足烯烴且方法中之溫度 為 100 C 。 ^布=薦莫耳/莫耳.小時之平均速率以⑽選擇性完 王轉化成丁酸甲@旨而22%選擇性轉化成2•甲基丙 。 例5 重覆例2,然而使用2 〇毫升之 Γ 笔开心a - Cl4烯烴。在3小時後 冷却熱壓器。 · a - C i 4晞烴在2 5 0莫耳/葺耳|咕、 矢卄旲斗.小時〈平均速率以δ0%選 擇性轉化95%成線型甲基酯。 例6 重覆例2,然而使用2 〇毫升之内_ Γ ^ 、、、 。 毛万 < 叫Lu烯烴,且方法中之 溫度為115°C而一氧化碳爆力乂 1〇 p ^ 又!刀為iU巴。在5小時後冷却熱 12- 本纸張尺度適用中國國家標準(CNS)A4規格(210X297公釐) (请先閲讀背面之注意事項再填寫本頁) 訂 f 528759 A7 B7 >選擇性 五、發明説明(10) 壓器 内婦烴在120莫耳/莫耳小時 玄 4吁足十均速率以78%· 轉化93%成線型甲基酯。
比較例A 二’然而使用1,3_雙(二-第三丁基磷酿基)丙燒為 配位基並在-氧化碳壓力各別為lQ和3q巴。 德 冷却熱壓器。 + # < 内烯烴在5莫耳/莫耳.小時 <平均速率以7 5 °/。選擇性僅 只轉化1 0 %成線型甲基酯。 · 例7 重覆例2 ,然而使用1 〇赛斗, 人仏、u .笔升·3-戍埽酸甲酯為不飽和化 合物,万法中之溫度為115 °c且-氧化碳壓力為15巴。6 小時後冷却熱壓器。 ,3-戊烯酸甲酯在i⑽莫耳/莫耳小時之平均速率以84% 選擇性完全轉化成線型二甲基醋。 例8 · 重復例2然而使用0.1毫莫耳丙酮酸乙醯鉑,0丨2毫 旲耳DPA3與0.25毫莫耳MSA。此外,將熱壓器中之成份 加熱至125 C。3小時後冷却熱壓器。 乙婦在5 0 0莫耳/莫耳.小時之平均速率以工〇 〇 %選擇性完 全轉化成丙酸甲酯。
比較例B 重覆例8,然而使用丨,%雙(二_第三丁基磷醯基)丙烷為 配位基。 . 13- 本紙張尺度適用中國國家標準(CNS ) M規格(2丨〇>< 297公釐) (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部中央標準局員工消費合作社印製 申請曰期 <^]s i Λ 案 號 87105264 類 別 以上各欄由本局填ΐέ ) 中文說明書修正本(88年2月).:/ A4 C4 528759 霧黑專利説明書 中 文 含一2-磷-三環〔3.3.1.1.{3/7}〕癸基之二膦化物 發明 新型 名稱 英 文
DIPHOSPHINES CONTAINING A 2-PHOSPHA-TRICYCLO 〔3.3.1·1.{3,7}〕DECYL GROUP 姓 名 1. 艾特德蘭特 2. 保羅吉拉德普林哥. .傑可包凱薩琳娜露西亞瓊安娜蘇克布柯 國 籍 1,3均荷蘭 2英國 裝 發明 創作 人 住、居所 ].荷蘭阿姆斯特丹市貝得惠斯路3號 2. 英國普利斯托市肯托克斯十字路 3. 荷蘭阿姆斯特丹市貝得惠斯路3號 訂 姓 名 (名稱) 荷蘭商蜆殼國際研究所 線 經濟部中央標準局員工消費合作社印^i 申請人 國 籍 住、居所 (事務所) 代表人 姓 名 荷蘭 荷蘭海牙市卡爾文拜蘭特俞30號 瓊安尼斯亞特凡朱帝芬 本纸張尺度適用中國國家標準(CNS ) A4規;( 210X 297公釐) 528759 第87105264號專利申請案¥ 3月8日修正/更正/補充 中文說明書修正頁(91年3月) A7 — --—— B7 五、發明説明(8 ) 笔升熱壓為中進行。用於表中之縮寫有以下意義: DPA2=1,2-P,p’_ 二(2-磷-ns,?-四甲基-6,9,1〇-三氧 三環[3·3·1·1{3,7}癸基)乙烷 〇?八3=1,3-?,?’-二(2_磷_1,3,5,7-四甲基-6,91〇-三氧 三環[3.3·1·1{3,7}癸基)丙烷 MS Α=曱橫酸 例1 (配位某々厶占i) 將4.63愛莫耳二膦基丙烷加入含27·8毫莫耳2,4-戊二酮 < 20晕升5Μ HC1溶液中。經1小時攪拌後,白色固體開 始沉殿。另外再攪拌反應混合物24小時,再將揮發組份移 除而留下白色、在空氣中穩定之固體產物。產物以水洗滌 (6 X 2 0毫升)、溶於2 〇亳升二氯甲烷再以硫酸鎂乾燥。過 遽溶液並在真空中濃縮成1毫升。將1〇毫升戊烷加入以沉 澱純化產物再將之回收(〇_75克,34%產量)。 4 NMR (400 ΜΗζ,在 CD2C12),5 1.18 (6Η,s),5 1·22 (18H,s),δ 1·4-4·9 (m,14H) ; 31P NMR (162 MHz) : (5-30.0, -30.8 ppm ;質譜儀顯示m/e 472(M+)。此些數據確認產物 特性。 以相同方式製備DP A2,然而,使用二膦基乙烷代替二膦 基丙燒。 例2 (羰基化作用) 熱壓器中填裝50毫升甲醇、〇·;[毫莫耳醋酸鈀(11)〇15 毫莫耳DPA3、和〇·2毫莫耳MSA。沖洗後,以一氧化碳和 乙烯加壓熱壓器,使其分壓各自為3 〇巴和2〇巴。接著 -11 - 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公爱) 528759 第87105264號專利申請案犯年q月日修正/更正/補名 中文說明書修正頁(91年3月)A爭
而現今丙酸甲酯僅在10莫耳/莫耳·小時之平均速率形 成。 . 例9(醛化作用) 熱壓咨中填充50亳升二乙二醇二甲醚,〇1毫莫耳丙酮 酸乙醯二羰基铑與〇·12毫莫耳DPA3。沖洗後,將熱壓器 填充15笔升丙婦並以一氧化碳和氫氣加壓至每一者分壓為 25巴和25巴。接著封住反應器。將熱壓器成份加熱至 C並在此溫度維持〇·25小時。冷却後,由熱壓器成份中取 出樣品並以GLC分析。 丙烯以4000莫耳/莫耳·小時之平均速率完全轉化成丁醛 和2 -甲基丙駿(莫耳比為4 8 : 5 2 )混合物。 例10 重覆例9,然而使用〇1毫莫耳dPA2。 現則丙晞以5000莫耳/莫耳·小時之平均速率完全轉化成 丁駿和2 -甲基丙醛(莫耳比為49 : 51)混合物。 例1 1 重覆例9,然而使用丨〇毫升醋酸乙晞酯代替丙烯,5 〇亳 升甲苯代替二乙二醇二甲醚和〇2毫莫耳DpA3。此外將熱 壓器加熱至115°C之溫度。 、醋酸乙晞酯在5000莫耳/莫耳·小時之平均速率完全轉化 成醋酸1-曱醯酯乙酯和醋酸2 -曱醯酯乙酯(莫耳比為1〇 · 1)混合物。 _ - 14-
本紙張度適用中國國豕標準(Cns) A4規格(2i〇X297公爱)
Claims (1)
- 528759=87105264號專利申請案 中文申請專利範圍修正本(91年3月) A8I B8 C8 ;日修正/更正/補充種下式之二膦化物 R1>p-r2-p<r /、中R代表伸乙基或伸丙基,R 1代表與所連接之磷原子 —起成為視需要經取代之2 -磷-三環[3 · 3 . 1 . 1 { 3,7 癸基 或其衍生物之二價基團,其中一或多個碳原子係經雜原 子取代。 2.根據申請專利範圍第1項之二膦化物,其中該2 _磷-三環 [3 · 3 · 1 · 1 { 3,7 }]癸基係被具有至高2 0個原子之單價基R5 在I 3,5或7位置中之一或多個之上取代。 3·根據申凊專利範圍第2項之二膦化物,其中2 _磷_三環 [3·3.1·1{3,7}]爹基係在每一個1,3,5和7之位置上被 相同之R5基取代。 4·根據申請專利範圍第3項之二膦化物,其中該R5為甲基。 5·根據申請專利範圍第1至4項中任一項之二膦化物,其中 2-石粦-三環[3·3.1 ·1{3,7}]癸基在其骨架6,9和10之位 且上具有氧和/或硫原子。 6·根據申請專利範圍第5項之二膦化物,其中2_磷-三環 [3*3.1.1{3,7}]癸基為2-磷-1,3,5,7-四甲基-6,9,10-三氧三環〔3·3·1·1·{3·7}〕癸基。 7·根據申請專利範圍第6項之二膦化物,其中之配位基是選 自 1,2-Ρ,Ρ’ -二(2 -磷·ι,3,5,7 -四甲基-6,9,10 -三氧三環 [3·3·1_1{3,7}]癸基)乙燒(DPA2)或 1,3-Ρ,Ρ,-二(2-磷-1,3,5,7-四甲基-6,9,10-三氧三環[3.3.1.1{3,7}]癸 基)丙烷(D P A 3 )。 本紙張尺度適用tie家料(CNS) A4規格(210X297公釐) 528759 A8 B8 C8 申請專利範圍 8· —種羰基化催化劑,其可經由組合以下物質而得: (i)選自元素週期表第8、9或10族之金屬陽離子,和 (i i)根據申請專利範圍第1項之二膦化物。 9·根據申請專利範圍第8項之羰基化催化劑,其中金屬陽離 子為第9族金屬陽離子或第1〇族金屬陽離子。 1〇·根據申請專利範圍第9項之羰基化催化劑,其中金屬陽離 子為Rh、Pd或Pt。 11· 一種使不飽和化合物羰基化之方法,其係經由與一氧化 碳及共同反應物反應而成,其中係使用根據申請專利範 圍第8、9或1 〇項中任一項之羰基化催化劑。 12·根據申請專利範圍第12項之方法,其中不飽和化合物為 每分子具有2至3 0個碳原子之乙晞系不飽和化合物。 13·根據申請專利範圍第12項之方法,其中乙稀系不飽和化 合物為每分子具有2至22個碳原子之α -或内部婦烴。 Η·根據申請專利範圍第i i至丨3項中任一項之方法,其中共 同反應物為分子氫,每分子具有丨至6個碳原子之單羥 -2-
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TW528759B true TW528759B (en) | 2003-04-21 |
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ID=26147366
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW087105264A TW528759B (en) | 1997-03-26 | 1998-04-08 | Diphosphines containing a 2-phospha-tricyclo [3.3.1.1.{3,7}] decyl group |
Country Status (7)
Country | Link |
---|---|
US (1) | US6156934A (zh) |
EP (1) | EP0971940B1 (zh) |
JP (1) | JP4201846B2 (zh) |
AU (1) | AU7428498A (zh) |
DE (1) | DE69805789T2 (zh) |
TW (1) | TW528759B (zh) |
WO (1) | WO1998042717A1 (zh) |
Families Citing this family (38)
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US6545192B2 (en) * | 1999-05-11 | 2003-04-08 | Shell Oil Company | Process for separating olefins from saturated hydrocarbons |
WO2001028972A1 (en) * | 1999-10-22 | 2001-04-26 | Shell Internationale Research Maatschappij B.V. | Process for the carbonylation of an acetylenically unsaturated compound |
US6706912B2 (en) | 2000-03-14 | 2004-03-16 | Shell Oil Company | Process for the carbonylation of ethylenically unsaturated compounds |
US6743911B2 (en) † | 2000-03-14 | 2004-06-01 | Shell Oil Company | Process for the carbonylation of pentenenitrile |
DE10023470A1 (de) * | 2000-05-12 | 2001-11-15 | Basf Ag | Verfahren zur Herstellung von Aldehyden |
DE10023468A1 (de) | 2000-05-12 | 2001-11-15 | Basf Ag | Verfahren zur Hydroformylierung ethylenisch ungesättigter Verbindungen und Ligand-Metall-Komplex als Katalysator hierfür |
MY127093A (en) * | 2000-05-17 | 2006-11-30 | Lucite Int Uk Ltd | Bidentate ligands useful in catalyst systems |
DE10033982A1 (de) * | 2000-07-13 | 2002-01-24 | Basf Ag | Verfahren zur Herstellung von Additionsprodukten ethylenisch ungesättigter Verbindungen |
DE10048874A1 (de) | 2000-09-29 | 2002-04-11 | Basf Ag | Katalysatorsystem und Verfahren zur Carbonylierung |
DE10060313A1 (de) * | 2000-12-04 | 2002-06-13 | Basf Ag | Verfahren zur Carbonylierung von Pentensäure und deren Derivate |
JP2004515537A (ja) * | 2000-12-11 | 2004-05-27 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 5−シアノ吉草酸、アジピン酸、またはアジピン酸ジメチルの製造方法 |
DE10106348A1 (de) | 2001-02-09 | 2002-08-14 | Basf Ag | Als Katalysator oder zur Herstellung eines Katalysatorsystems geeignete Verbindung |
TW592819B (en) | 2001-05-18 | 2004-06-21 | Kevin Dale Allen | One-step production of 1,3-propanediol from ethylene oxide and syngas with a cobalt-iron catalyst |
DE10228293A1 (de) | 2001-07-28 | 2003-02-13 | Basf Ag | Verfahren zur Herstellung von Dialkylketonen |
DE10148712A1 (de) | 2001-10-02 | 2003-04-17 | Basf Ag | Diphosphin |
CN1308337C (zh) * | 2001-11-09 | 2007-04-04 | 国际壳牌研究有限公司 | 用于不饱和化合物羰基化的双齿配位体 |
US20030105348A1 (en) | 2001-11-19 | 2003-06-05 | Bunel Emilio E. | Process for making 5-cyanovaleric acid, adipic acid or dimethyl adipate |
AU2003210312A1 (en) * | 2002-02-19 | 2003-09-09 | Shell Internationale Research Maatschappij B.V. | Processes for the preparation of a carobxylic anhydride and use of the carboxylic anhydride as an acylation agent |
WO2003070370A1 (en) * | 2002-02-19 | 2003-08-28 | Shell Internationale Research Maatschappij B.V. | Process for the carbonylation of an ethylenically unsaturated compound and catalyst therefore |
GB0218613D0 (en) * | 2002-08-10 | 2002-09-18 | Lucite Int Uk Ltd | Process for the carbonylation of ethylenically unsaturated compounds |
CN1684931A (zh) | 2002-09-26 | 2005-10-19 | 国际壳牌研究有限公司 | 伯醇的制备方法 |
EP1651587A1 (en) | 2003-07-03 | 2006-05-03 | Lucite International UK Limited | Process for the hydroformylation of ethylenically unsaturated compounds |
GB0403592D0 (en) | 2004-02-18 | 2004-03-24 | Lucite Int Uk Ltd | A catalyst system |
US7265242B2 (en) | 2004-02-26 | 2007-09-04 | Shell Oil Company | Process for the carbonylation of ethylenically or acetylenically unsaturated compounds |
GB0411951D0 (en) * | 2004-05-28 | 2004-06-30 | Lucite Int Uk Ltd | Carbonylation of ester |
GB0516556D0 (en) | 2005-08-12 | 2005-09-21 | Lucite Int Uk Ltd | Improved catalyst system |
AU2006314268C1 (en) | 2005-11-17 | 2014-01-09 | Lucite International Uk Limited | Carbonylation of ethylenically unsaturated compounds |
GB0607494D0 (en) | 2006-04-13 | 2006-05-24 | Lucite Int Uk Ltd | Metal complexes |
JP2010511600A (ja) * | 2006-12-02 | 2010-04-15 | ルーサイト インターナショナル ユーケー リミテッド | 新規のカルボニル化配位子及びエチレン性不飽和化合物のカルボニル化におけるその使用 |
GB0625518D0 (en) * | 2006-12-21 | 2007-01-31 | Lucite Int Uk Ltd | Carbonylation of conjugated dienes |
GB0713624D0 (en) * | 2007-07-13 | 2007-08-22 | Lucite Int Uk Ltd | Improved solvent for catalyst system |
GB0812297D0 (en) * | 2008-07-04 | 2008-08-13 | Lucite Int Uk Ltd | Novel carbonylation ligand sand thier use of in the carbonylation of ethylenically unsaturated compounds |
GB2467163B (en) * | 2009-01-26 | 2013-11-06 | Rhodia Operations | Ligands |
FR2943061B1 (fr) * | 2009-03-13 | 2011-02-25 | Rhodia Operations | Composes organophosphores, systemes catalytiques comprenant ces composes et procede d'hydrocyanation ou d'hydroformylation utilisant ces systemes catalytiques |
GB0921875D0 (en) | 2009-12-15 | 2010-01-27 | Lucite Int Uk Ltd | A continuous process for the carbonylation of ethylene |
US20120309613A1 (en) | 2009-12-15 | 2012-12-06 | Lucite International Uk Limited | Carbonylation process |
GB201000078D0 (en) | 2010-01-05 | 2010-02-17 | Lucite Int Uk Ltd | Process for the carbonylation of ethylenically unsaturated compounds, novel carbonylation ligands and catalyst systems incorporatng such ligands |
GB201122054D0 (en) | 2011-12-21 | 2012-02-01 | Lucite Int Uk Ltd | A continuous process for the carbonylation of ethylene |
Family Cites Families (8)
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US3026327A (en) * | 1960-07-06 | 1962-03-20 | American Cyanamid Co | Substituted 1, 3, 5, 7-tetraalkyl-2, 6, 9-trioxa-10-phosphatricyclo [3.3.1.1.3,7] decanes |
GB1127965A (en) * | 1965-11-26 | 1968-09-25 | Shell Int Research | Ditertiary phosphines and application thereof as catalyst components for alcohol production |
US4230641A (en) * | 1977-11-21 | 1980-10-28 | Air Products And Chemicals, Inc. | Hydroformylation of olefins |
US4946560A (en) * | 1988-10-27 | 1990-08-07 | Shell Oil Company | Process for separating alpha and internal olefins |
US4915794A (en) * | 1988-10-27 | 1990-04-10 | Shell Oil Company | Process for converting internal olefins to alpha olefins |
US5012034A (en) * | 1989-08-07 | 1991-04-30 | Shell Oil Company | Process for separating styrene from styrene-containing hydrocarbon streams |
DE69210054T2 (de) * | 1991-01-15 | 1996-12-12 | Shell Int Research | Carbonylierung von Olefinen |
DE69409651T2 (de) * | 1993-07-19 | 1998-08-06 | Shell Int Research | Verfahren zur carbonylierung von acetylenisch ungesättigten verbindungen |
-
1997
- 1997-12-09 US US08/987,555 patent/US6156934A/en not_active Expired - Lifetime
-
1998
- 1998-03-25 JP JP54443498A patent/JP4201846B2/ja not_active Expired - Fee Related
- 1998-03-25 AU AU74284/98A patent/AU7428498A/en not_active Abandoned
- 1998-03-25 EP EP98921417A patent/EP0971940B1/en not_active Expired - Lifetime
- 1998-03-25 DE DE69805789T patent/DE69805789T2/de not_active Expired - Lifetime
- 1998-03-25 WO PCT/EP1998/001916 patent/WO1998042717A1/en active IP Right Grant
- 1998-04-08 TW TW087105264A patent/TW528759B/zh active
Also Published As
Publication number | Publication date |
---|---|
EP0971940B1 (en) | 2002-06-05 |
US6156934A (en) | 2000-12-05 |
EP0971940A1 (en) | 2000-01-19 |
JP4201846B2 (ja) | 2008-12-24 |
AU7428498A (en) | 1998-10-20 |
JP2001520659A (ja) | 2001-10-30 |
DE69805789D1 (de) | 2002-07-11 |
WO1998042717A1 (en) | 1998-10-01 |
DE69805789T2 (de) | 2003-01-02 |
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