JP5376743B2 - アダマンチル基を有するホスファンリガンド、その製造および接触反応におけるその使用 - Google Patents
アダマンチル基を有するホスファンリガンド、その製造および接触反応におけるその使用 Download PDFInfo
- Publication number
- JP5376743B2 JP5376743B2 JP2002515907A JP2002515907A JP5376743B2 JP 5376743 B2 JP5376743 B2 JP 5376743B2 JP 2002515907 A JP2002515907 A JP 2002515907A JP 2002515907 A JP2002515907 A JP 2002515907A JP 5376743 B2 JP5376743 B2 JP 5376743B2
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- JP
- Japan
- Prior art keywords
- adamantyl
- transition metal
- ligand
- alkyl
- phosphane
- 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.)
- Expired - Lifetime
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- 239000003446 ligand Substances 0.000 title claims abstract description 62
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 title claims description 37
- 238000006555 catalytic reaction Methods 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 37
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000003624 transition metals Chemical class 0.000 claims abstract description 25
- 230000003197 catalytic effect Effects 0.000 claims abstract description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 43
- -1 adamantyl phosphane Chemical compound 0.000 claims description 32
- 125000000217 alkyl group Chemical group 0.000 claims description 31
- 229910000064 phosphane Inorganic materials 0.000 claims description 30
- 239000005922 Phosphane Substances 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 229910052763 palladium Inorganic materials 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 125000004437 phosphorous atom Chemical group 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 8
- 150000001502 aryl halides Chemical class 0.000 claims description 7
- 238000005810 carbonylation reaction Methods 0.000 claims description 7
- 238000011065 in-situ storage Methods 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 150000001345 alkine derivatives Chemical class 0.000 claims description 6
- 230000006315 carbonylation Effects 0.000 claims description 6
- 230000000737 periodic effect Effects 0.000 claims description 6
- 238000007341 Heck reaction Methods 0.000 claims description 5
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 238000005576 amination reaction Methods 0.000 claims description 3
- 150000005347 biaryls Chemical class 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical class PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002816 nickel compounds Chemical class 0.000 claims description 2
- 125000002524 organometallic group Chemical group 0.000 claims description 2
- 150000002941 palladium compounds Chemical class 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 150000003623 transition metal compounds Chemical class 0.000 claims description 2
- ITHPEWAHFNDNIO-UHFFFAOYSA-N triphosphane Chemical class PPP ITHPEWAHFNDNIO-UHFFFAOYSA-N 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 7
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims 7
- 150000004696 coordination complex Chemical class 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract description 2
- 238000007670 refining Methods 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 42
- 239000000203 mixture Substances 0.000 description 38
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 239000000243 solution Substances 0.000 description 33
- 239000000047 product Substances 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- 238000010992 reflux Methods 0.000 description 13
- HTJWUNNIRKDDIV-UHFFFAOYSA-N bis(1-adamantyl)-butylphosphane Chemical compound C1C(C2)CC(C3)CC2CC13P(CCCC)C1(C2)CC(C3)CC2CC3C1 HTJWUNNIRKDDIV-UHFFFAOYSA-N 0.000 description 12
- 239000012074 organic phase Substances 0.000 description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 125000002947 alkylene group Chemical group 0.000 description 7
- RRRZOLBZYZWQBZ-UHFFFAOYSA-N bis(1-adamantyl)phosphane Chemical compound C1C(C2)CC(C3)CC2CC13PC(C1)(C2)CC3CC2CC1C3 RRRZOLBZYZWQBZ-UHFFFAOYSA-N 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 7
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical class [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 description 7
- 235000011152 sodium sulphate Nutrition 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 5
- GUJMRFZLPFIYFI-UHFFFAOYSA-N bis(1-adamantyl)-hexylphosphane Chemical compound C1C(C2)CC(C3)CC2CC13P(CCCCCC)C1(C2)CC(C3)CC2CC3C1 GUJMRFZLPFIYFI-UHFFFAOYSA-N 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 5
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 239000013067 intermediate product Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000000607 proton-decoupled 31P nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 229920002545 silicone oil Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 125000004434 sulfur atom Chemical group 0.000 description 5
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- VDUWTDKCQAOGBW-UHFFFAOYSA-N bis(1-adamantyl)-methylphosphane Chemical compound C1C(C2)CC(C3)CC2CC13P(C)C1(C2)CC(C3)CC2CC3C1 VDUWTDKCQAOGBW-UHFFFAOYSA-N 0.000 description 4
- 125000001072 heteroaryl group Chemical group 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- KZVBBTZJMSWGTK-UHFFFAOYSA-N 1-[2-(2-butoxyethoxy)ethoxy]butane Chemical compound CCCCOCCOCCOCCCC KZVBBTZJMSWGTK-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 150000001500 aryl chlorides Chemical class 0.000 description 3
- 238000006254 arylation reaction Methods 0.000 description 3
- KZPMJOMGOVFHOK-UHFFFAOYSA-N bis(1-adamantyl)-[3-[bis(1-adamantyl)phosphanyl]butan-2-yl]phosphane Chemical compound C1C(C2)CC(C3)CC2CC13P(C12CC3CC(CC(C3)C1)C2)C(C)C(C)P(C12CC3CC(CC(C3)C1)C2)C1(C2)CC(C3)CC2CC3C1 KZPMJOMGOVFHOK-UHFFFAOYSA-N 0.000 description 3
- ANIAFEJRWQDKDV-UHFFFAOYSA-N bis(1-adamantyl)-benzylphosphane Chemical compound C1C(C2)CC(C3)CC2CC13P(C12CC3CC(CC(C3)C1)C2)CC1=CC=CC=C1 ANIAFEJRWQDKDV-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 150000003002 phosphanes Chemical class 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 2
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalene Chemical class C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 2
- AYFJBMBVXWNYLT-UHFFFAOYSA-N 2-bromo-6-methoxynaphthalene Chemical compound C1=C(Br)C=CC2=CC(OC)=CC=C21 AYFJBMBVXWNYLT-UHFFFAOYSA-N 0.000 description 2
- KJZUMKZNMHYVIY-UHFFFAOYSA-N 3-[bis(1-adamantyl)phosphanyl]-n,n-dimethylpropan-1-amine Chemical compound C1C(C2)CC(C3)CC2CC13P(CCCN(C)C)C1(C2)CC(C3)CC2CC3C1 KJZUMKZNMHYVIY-UHFFFAOYSA-N 0.000 description 2
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 238000005905 alkynylation reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BVOJCPQWSXCCKU-UHFFFAOYSA-N bis(1-adamantyl)-chlorophosphane Chemical compound C1C(C2)CC(C3)CC2CC13P(Cl)C1(C2)CC(C3)CC2CC3C1 BVOJCPQWSXCCKU-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical compound ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000006772 olefination reaction Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 description 1
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 1
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 description 1
- RTFVOXURDFZPKR-UHFFFAOYSA-N 1-[1-adamantyl(chloro)phosphoryl]adamantane Chemical compound C1C(C2)CC(C3)CC2CC13P(=O)(Cl)C1(C2)CC(C3)CC2CC3C1 RTFVOXURDFZPKR-UHFFFAOYSA-N 0.000 description 1
- AVVOZVZKWKNBTK-UHFFFAOYSA-N 1-adamantyl(dicyclohexyl)phosphane Chemical compound C1CCCCC1P(C12CC3CC(CC(C3)C1)C2)C1CCCCC1 AVVOZVZKWKNBTK-UHFFFAOYSA-N 0.000 description 1
- JKGPULQIZNLFQN-UHFFFAOYSA-N 1-adamantyl(ditert-butyl)phosphane Chemical compound C1C(C2)CC3CC2CC1(P(C(C)(C)C)C(C)(C)C)C3 JKGPULQIZNLFQN-UHFFFAOYSA-N 0.000 description 1
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- YRGAYAGBVIXNAQ-UHFFFAOYSA-N 1-chloro-4-methoxybenzene Chemical compound COC1=CC=C(Cl)C=C1 YRGAYAGBVIXNAQ-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- KBIAVTUACPKPFJ-UHFFFAOYSA-N 1-ethynyl-4-methoxybenzene Chemical group COC1=CC=C(C#C)C=C1 KBIAVTUACPKPFJ-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- WKSZGSWQSATION-UHFFFAOYSA-N 2-adamantyl(dibutyl)phosphane Chemical compound C1C(C2)CC3CC1C(P(CCCC)CCCC)C2C3 WKSZGSWQSATION-UHFFFAOYSA-N 0.000 description 1
- DGQUMYDUFBBKPK-UHFFFAOYSA-N 2-ethenyl-6-methoxynaphthalene Chemical compound C1=C(C=C)C=CC2=CC(OC)=CC=C21 DGQUMYDUFBBKPK-UHFFFAOYSA-N 0.000 description 1
- LJQNMDZRCXJETK-UHFFFAOYSA-N 3-chloro-n,n-dimethylpropan-1-amine;hydron;chloride Chemical compound Cl.CN(C)CCCCl LJQNMDZRCXJETK-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
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- IYPGZJCYILHNEU-UHFFFAOYSA-N bis(1-adamantyl)-propan-2-ylphosphane Chemical compound C1C(C2)CC(C3)CC2CC13P(C(C)C)C1(C2)CC(C3)CC2CC3C1 IYPGZJCYILHNEU-UHFFFAOYSA-N 0.000 description 1
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- UDVCTSICDMIKSD-UHFFFAOYSA-N bis(2-adamantyl)-butylphosphane Chemical compound C1C(CC2C3)CC3CC1C2P(CCCC)C1C(C2)CC3CC2CC1C3 UDVCTSICDMIKSD-UHFFFAOYSA-N 0.000 description 1
- HQWHQLTUUGIFMQ-UHFFFAOYSA-N bis(2-adamantyl)-cyclohexylphosphane Chemical compound C1CCCCC1P(C1C2CC3CC(C2)CC1C3)C1C(C2)CC3CC2CC1C3 HQWHQLTUUGIFMQ-UHFFFAOYSA-N 0.000 description 1
- BULRRFXEYNENKW-UHFFFAOYSA-N bis(2-adamantyl)-propan-2-ylphosphane Chemical compound C1C(CC2C3)CC3CC1C2P(C(C)C)C1C(C2)CC3CC2CC1C3 BULRRFXEYNENKW-UHFFFAOYSA-N 0.000 description 1
- LWZDNMSWNQTTJZ-UHFFFAOYSA-N bis(2-adamantyl)-tert-butylphosphane Chemical compound C1C(CC2C3)CC3CC1C2P(C(C)(C)C)C1C(C2)CC3CC2CC1C3 LWZDNMSWNQTTJZ-UHFFFAOYSA-N 0.000 description 1
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- YVNXLZUFRHPSEV-UHFFFAOYSA-N butyl 6-methoxynaphthalene-2-carboxylate Chemical compound C1=C(OC)C=CC2=CC(C(=O)OCCCC)=CC=C21 YVNXLZUFRHPSEV-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
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- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
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- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- ZVSLRJWQDNRUDU-UHFFFAOYSA-L palladium(2+);propanoate Chemical compound [Pd+2].CCC([O-])=O.CCC([O-])=O ZVSLRJWQDNRUDU-UHFFFAOYSA-L 0.000 description 1
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- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-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
- 239000002304 perfume Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
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- 239000002861 polymer material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- YVPIXZAXKQWEOB-UHFFFAOYSA-N trimethyl-[2-(4-nitrophenyl)ethynyl]silane Chemical group C[Si](C)(C)C#CC1=CC=C([N+]([O-])=O)C=C1 YVPIXZAXKQWEOB-UHFFFAOYSA-N 0.000 description 1
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 description 1
- HYUFXBPAIGJHRY-UHFFFAOYSA-N triphenylphosphane;dihydrochloride Chemical compound Cl.Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 HYUFXBPAIGJHRY-UHFFFAOYSA-N 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
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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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
- B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
-
- C—CHEMISTRY; METALLURGY
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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
- C07B37/04—Substitution
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- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/023—Preparation; Separation; Stabilisation; Use of additives
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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Description
(アダマンチル)nP(アルキル)m Ia
(アダマンチル)o(アルキル)qP(アルキレン′)P(アダマンチル)r(アルキル)s Ib
[式中、アダマンチルは1位または2位で燐原子に結合したアダマンチル基(IIa、IIb):
アルキルはC1〜C18−アルキル基を表し、
アルキレン′は橋かけメチレン橋、1,2−エチレン橋、1,3−プロピレン橋、1,4−ブチレン橋、1,5−ペンチレン橋、1,6−ヘキシレン橋、1,2−ジフェニレン、2,2′−置換1,1′−ビナフチルまたはフェロセニル橋を表し、
アルキル基、アルキレン′基およびアダマンチル基は互いに独立に水素原子のほかに10個までの置換基を有することができ、これらの置換基は互いに独立にC1〜C8−アルキル、O−アルキル(C1〜C8)、OH、OCO−アルキル(C1〜C8)、O−フェニル、フェニル、アリール、フルオロ、NO2、Siアルキル(C1〜C8)3、CN、COOH、CHO、SO3H、NH2、NH−アルキル−(C1〜C8)、N−アルキル(C1〜C8)2、P(アルキル(C1〜C8)2、P(アリール)2、SO2−アルキル(C1〜C6)、SO−アルキル(C1〜C6)、CF3、NHCO−アルキル(C1〜C4)、COO−アルキル(C1〜C8)、CONH2、CO−アルキル(C1〜C8)、NHCHO、NHCOO−アルキル(C1〜C4)、CO−フェニル、COO−フェニル、CH=CH−CO2−アルキル(C1〜C8)、CH=CHCOOH、PO(フェニル)2、PO(アルキル(C1〜C4))2、PO3H2、PO(Oアルキル(C1〜C6))2、SO3(アルキル(C1〜C4))を表し、アリールは5〜14個の環炭素原子を有する芳香環を表し、1個以上の環炭素原子は窒素原子、酸素原子および/または硫黄原子により置換されていてもよく、1〜13個の環炭素原子を有する複素芳香環が存在し、
nは1〜3の数を表し、mは0〜2の数を表し、n+mが3である条件が満たされていなければならず、
oおよびrは1または2の数を表し、qおよびsは0または1の数を表し、o+qが2であり、r+sが2である条件が満たされていなければならない]で表される新規ホスファンリガンドの開発により解決される。
アルキル基、アルキレン′基およびアダマンチル基は互いに独立に水素原子のほかに3個までの置換基を有することができ、これらの置換基は互いに独立にC1〜C8−アルキル、O−アルキル(C1〜C8)、OH、OCO−アルキル(C1〜C8)、O−フェニル、フェニル、COOH、SO3H、NH2、P(アルキル(C1〜C8))2、P(フェニル)2、COO−アルキル(C1〜C8)、CONH2、PO(フェニル)2を表すことができる、本発明の式IaおよびIbの化合物が特に有利である。
ジ(1−アダマンチル)−メチルホスフィン、
ジ(1−アダマンチル)−イソプロピルホスフィン、
ジ(1−アダマンチル)−n−ブチルホスフィン、
ジ(1−アダマンチル)−t−ブチルホスフィン、
ジ(1−アダマンチル)−n−ヘキシルホスフィン、
ジ(1−アダマンチル)−シクロヘキシルホスフィン、
ジ(1−アダマンチル)−ベンジルホスフィン、
ジ(1−アダマンチル)−ペンタフルオロエチルホスフィン、
ジ(3−アミノ−アダマント−1−イル)−n−ブチルホスフィン、
ジ(3−アセチル−アダマント−1−イル)−n−ブチルホスフィン、
ジ[3−(p−ヒドロキシフェニル)−アダマント−1−イル]−メチルホスフィン、
ジ(2−アダマンチル)−イソプロピルホスフィン、
ジ(2−アダマンチル)−n−ブチルホスフィン、
ジ(2−アダマンチル)−t−ブチルホスフィン、
ジ(2−アダマンチル)−シクロヘキシルホスフィン
が製造できる。
(1−アダマンチル)−ジ−t−ブチルホスフィン、
(1−アダマンチル)−ジ−シクロヘキシルホスフィン、
(2−アダマンチル)−ジ−n−ブチルホスフィン
が製造できる。
1,2−ビス[ジ(1−アダマンチル)ホスフィノ}エタン、
1,4−ビス[ビス(1−アダマンチル)ホスフィノ]ブタン、
2,3−ビス[ジ(1−アダマンチル)ホスフィノ]ブタン、
4,5−ビス[ジ(1−アダマンチル)ホスフィノメチル]−2,2−ジメチル−1,3−ジオキソラン、
1,2−ビス[ジ(1−アダマンチル)ホスフィノ]ベンゼン
が製造できる。
以下の実施例は本発明を説明するために使用される。本発明は実施例に限定されない。
アダマンタン100g(0.73モル)、塩化アルミニウム(III)105g(0.79モル)および塩化燐(III)300mlの混合物を5時間還流した。過剰の塩化燐(III)を赤褐色の粘性の物質が残留するまで蒸留分離した。これをクロロホルム1リットル中で懸濁させた後で氷水1リットルで加水分解した。有機相を硫酸ナトリウム上で乾燥し、真空(0.1ミリバール)中で濃縮して乾燥した。
−14℃でトルエン600ml中のジ(1−アダマンチル)ホスフィン23g(76ミリモル)および1,8−ジアザビシクロ[5.4.0]ウンデカ−7−エン(DBU)14.5g(9.5ミリモル)の溶液に無水トルエン中のホスゲンの20%溶液60gを滴下し、室温に加熱後、なお16時間撹拌した。混合物を濾過し、溶剤を真空中で蒸留分離した。
例1
ジ(1−アダマンチル)−n−ブチルホスフィン(nBuPAd2)(変形1)
無水テトラヒドロフラン250ml中のジアダマンチルクロロホスフィン5.0g(15ミリモル)にヘキサン(18ミリモル)中のn−ブチルリチウムの1.6M溶液11mlを滴下した。この溶液を1時間還流した。真空中で溶剤を除去した後で残留物を真空中で蒸留した。ジアダマンチル−n−ブチルホスフィン2.6g(7.3ミリモル、49%)が得られた。
ジ(1−アダマンチル)ホスフィン4.6g(15ミリモル)をジ−n−ブチルエーテル50ml中に入れ、トルエン(50ミリモル)中のn−BuLiの2.5M溶液20mlを添加した。混合物を還流下に1時間沸騰させ、冷却し、1−ブチルブロミド4.1g(30ミリモル)を滴下した。混合物を還流下に30分沸騰させ、冷却し、塩化アンモニウム飽和溶液で洗浄し(3回)、有機相を分離し、硫酸ナトリウム上で乾燥し、減圧下で溶剤を蒸留分離した。
MS(E.I.70eV):m/z358(M+、12%);135(Ad+、100%)
MS(C.I.イソブテン):m/z359(M++H、100%)。
(変形3)
ジ(1−アダマンチル)クロロホスフィン1.5g(4.5ミリモル)を無水THF40ml中に入れ、撹拌下にヘキサン(8ミリモル)中の1.6M nBuLi溶液5mlを注入して添加した。混合物を還流下に2時間沸騰させ、減圧下で溶剤を蒸留分離し、残留物をバブル管中で蒸留した。
ジ(1−アダマンチル)ホスフィン4.6g(15ミリモル)をジ−n−ブチルエーテル50ml中に入れ、トルエン(50ミリモル)中のnBuLiの2.5M溶液20mlを添加した。混合物を還流下に1時間沸騰させ、冷却し、1−ブチルクロリド2.8g(30ミリモル)を滴下した。混合物を還流下に30分沸騰させ、冷却し、塩化アンモニウム飽和溶液で洗浄し(3回)、有機相を分離し、硫酸ナトリウム上で乾燥し、減圧下で溶剤を蒸留分離した。生成物をバブル管蒸留を使用して高い真空中で精製した。
ジ(1−アダマンチル)−メチルホスフィン(MeP(1−Ad)2)(変形1)
無水テトラヒドロフラン250ml中のジアダマンチルクロロホスフィン5.0g(15ミリモル)にヘキサン(18ミリモル)中のメチルリチウムの1.6M溶液11mlを滴下した。溶液を1時間還流した。真空中で溶剤を蒸留分離した後で残留物を真空中で蒸留した。ジアダマンチルメチルホスフィン2.3g(7.3ミリモル、49%)が得られた。
ジ(1−アダマンチル)クロロホスフィン2.0g(6.0ミリモル)を無水THF50mlに入れ、撹拌下にジエチルエーテル(8ミリモル)中の1.6MMeLi溶液5mlを注入して添加した。混合物を還流下に2時間沸騰させ、減圧下で溶剤を蒸留分離し、残留物をバブル管中で蒸留した。
元素分析:測定値(計算値);C:79.52%(79.70%)、H:10.60%(10.51%)、P:9.78%(9.79%)
31P{1H}−NMR(162.0MHz、C6D6、297K):δ=7.8
MS(E.I.70eV):m/z:316(M+、36%);135(Ad+、100%)
例3
ジ(1−アダマンチル)−n−ヘキシルホスフィン(HexP(1−Ad)2)(変形1)
無水テトラヒドロフラン150mlにマグネシウムくず0.45g(18ミリモル)を入れ、撹拌下で1−ブロモヘキサン3.0g(18ミリモル)と混合し、エーテルが加熱した。混合物を室温に冷却後、無水テトラヒドロフラン100ml中のジアダマンチルクロロホスフィン5.0g(15ミリモル)の溶液を滴下し、1時間還流した。真空中で溶剤を蒸留分離後、残留物を高い真空(0.01ミリバール)中で蒸留した。
ジ(1−アダマンチル)−n−ヘキシルホスフィン(HexP(1−Ad)2)(変形2)
ジ(1−アダマンチル)ホスフィン5.5g(18ミリモル)をジ−n−ブチルエーテル60mlに入れ、トルエン中のnBuLi(50ミリモル)の2.5M溶液20mlを添加した。混合物を還流下に45分沸騰させ、冷却し、1−ブロモヘキサン3.0g(18ミリモル)を滴下した。混合物を還流下に30分沸騰させ、冷却し、塩化アンモニウム飽和溶液で洗浄し(3回)、有機相を分離し、硫酸ナトリウム上で乾燥し、減圧下で溶剤を蒸留分離した。
MS:386.31062.(計算値C26H43Pに関して386.31024)
例4
ビス(ジアダマンチルホスフィノ)ブタン(ブチレン(PAd2)2)
無水テトラヒドロフラン150ml中にマグネシウムくず0.45g(18ミリモル)を入れ、撹拌下に1,4−ジブロモブタン2.0g(9.3ミリモル)と混合し、エーテルが加熱した。混合物を室温に冷却後、無水テトラヒドロフラン100ml中のジアダマンチルクロロホスフィン5.0g(15ミリモル)の溶液を滴下し、1時間還流した。真空中で溶剤を蒸留分離後、残留物を高い真空(0.01ミリバール)中で蒸留した。
ジ(1−アダマンチル)−3−ジメチルアミノプロピルホスフィン
ジ(1−アダマンチル)ホスフィン5.1g(17ミリモル)をジ−n−ブチルエーテル50mlに入れ、トルエン中のnBuLi(50ミリモル)の2.5M溶液20mlを添加した。混合物を還流下に1時間沸騰させ、冷却し、氷浴中で冷却しながら3−ジメチルアミノプロピルクロリド塩酸塩5.0g(31ミリモル)を添加した。混合物を還流下に30分沸騰させ、冷却し、塩化アンモニウム飽和溶液で洗浄し(3回)、有機相を分離し、硫酸ナトリウム上で乾燥し、減圧下で溶剤を蒸留分離した。
31P{1H}−NMR(162.0MHz、C6D6、297K):δ=24.5
MS:387.30528(計算値C25H42NPに関して387.30548)
例6
ジ(1−アダマンチル)−ベンジルホスフィン
ジ(1−アダマンチル)ホスフィン4.0g(13ミリモル)をジ−n−ブチルエーテル50mlに入れ、トルエン中のnBuLi(45ミリモル)の2.5M溶液18mlを添加した。混合物を還流下に30分沸騰させ、冷却し、ベンジルブロミド3.2g(19ミリモル)を滴下した。混合物を還流下に30分沸騰させ、冷却し、塩化アンモニウム飽和溶液で洗浄し(3回)、有機相を分離し、硫酸ナトリウム上で乾燥し、減圧下で溶剤を蒸留分離した。
MS:392.26420(計算値C27H37Pに関して392.26328)
例7〜20
ヘック反応の一般的な作業工程
圧力管(例えばAldrich社の製品)中で、アルゴン雰囲気下で、アリールハロゲニド5ミリモル、オレフィン6ミリモル、塩基6ミリモル、適当な量のリガンドおよびパラジウム(0)−dba錯体およびジエチレングリコール−n−ブチルエーテル500mg(GC分析の内部標準として)を無水ジオキサン5mlに添加した。管を閉鎖し、120℃の熱いシリコーン油浴中に懸濁した。24時間後、室温に冷却した。固形物を塩化メチレン5mlおよび2n塩酸5mlに溶解した。有機相をガスクロマトグラフィーにより分析した。生成物を蒸留、メタノール/アセトン混合物からの晶出またはカラムクロマトグラフィー(シリカゲル、ヘキサン/酢酸エチル混合物)により単離した。
スズキ反応の一般的な作業工程
圧力管(例えばAldrich社の製品)中で、アルゴン雰囲気下で、アリールハロゲニド3ミリモル、フェニルホウ酸4.5ミリモル、塩基6ミリモル、適当な量のリガンドおよびパラジウム(II)アセテート(P/Pd=2:1)およびヘキサデカン100mg(GC分析の内部標準として)を無水トルエン6mlに溶解した。管を閉鎖し、100℃の熱いシリコーン油浴中に懸濁した。20時間後、室温に冷却した。固形物を塩化メチレン10mlおよび希釈した水酸化ナトリウム溶液10mlに溶解した。有機相をガスクロマトグラフィーにより分析した。生成物をメタノール/アセトン混合物からの晶出またはカラムクロマトグラフィー(シリカゲル、ヘキサン/酢酸エチル混合物)により単離した。
接触アミノ化の一般的な作業工程
圧力管(例えばAldrich社の製品)中で、アルゴン雰囲気下で、アリールハロゲニド5ミリモル、アミン6ミリモル、ナトリウム−t−ブチレート6ミリモル、適当な量のリガンドおよびパラジウム(0)−ジベンジリデンアセトン錯体を無水トルエン5mlに添加した。管を閉鎖し、120℃の熱いシリコーン油浴中に懸濁した。20時間後、室温に冷却した。固形物を塩化メチレン5mlおよび2n塩酸5mlに溶解し、内部GC標準としてジエチレングリコール−ジ−n−ブチルエーテル500mgを添加した。有機相をガスクロマトグラフィーにより分析した。生成物を蒸留、メタノール/アセトン混合物からの晶出またはカラムクロマトグラフィー(シリカゲル、ヘキサン/酢酸エチル混合物)により単離した。
接触ケトン−α−アリール化
圧力管(例えばAldrich社の製品)中で、アルゴン雰囲気下で、アリールハロゲニド5ミリモル、ケトン6ミリモル、ナトリウム−t−ブチレート6ミリモル、適当な量のリガンドおよびパラジウム(II)−アセテートを無水トルエン5mlに添加した。管を閉鎖し、80℃の熱いシリコーン油浴中に懸濁した。20時間後、室温に冷却した。固形物を塩化メチレン5mlおよび2n塩酸5mlに溶解し、内部GC標準としてジエチレングリコール−ジ−n−ブチルエーテル500mgを添加した。有機相をガスクロマトグラフィーにより分析した。生成物を蒸留、メタノール/アセトン混合物からの晶出またはカラムクロマトグラフィー(シリカゲル、ヘキサン/酢酸エチル混合物)により単離した。
他の接触ケトン−α−アリール化の例
圧力管(例えばAldrich社の製品)中で、アルゴン雰囲気下で、アリールハロゲニド5ミリモル、ケトン6ミリモル、トリカリウムホスフェート6ミリモル、適当な量のリガンドおよびパラジウム(II)−アセテートを無水ジオキサン5mlに添加した。管を閉鎖し、100℃の熱いシリコーン油浴中に懸濁した。20時間後、室温に冷却した。固形物を塩化メチレン5mlおよび2n塩酸5mlに溶解し、内部GC標準としてジエチレングリコール−ジ−n−ブチルエーテル500mgを添加した。有機相をガスクロマトグラフィーにより分析した。生成物を蒸留、メタノール/アセトン混合物からの晶出またはカラムクロマトグラフィー(シリカゲル、ヘキサン/酢酸エチル混合物)により単離した。
アリールクロリドと亜鉛有機化合物のカップリング
エチニルリチウム−エチレンジアミン錯体50ミリモルの懸濁液を、0℃、THF40ml中で水不含の塩化亜鉛50ミリモル(THF40mlに溶解した)と混合した。30分で室温に加熱後、溶液を再び0℃に冷却し、4−クロロアニソール40ミリモルおよびPd(OAc)20.05モル%およびブチルジアダマンチルホスフィン0.1モル%と混合した。反応混合物を25〜50℃で完全に反応するまで撹拌した。引き続き溶液を2MHCl溶液と混合した。エーテルで抽出後、エーテル相を洗浄し、蒸留し、p−メトキシフェニルアセチレン76%が得られた。
アルキンとのカップリング
ジエチルアミン40ml中のトリメチルシリルアセチレン12ミリモルおよび4−クロロニトロベンゼン10ミリモルの混合物をPd(OAc)20.005モル%、ヘキシルジアダマンチルホスフィン0.01モル%およびヨウ化銅(I)1モル%と混合した。混合物を還流下に完全に反応するまで撹拌した。引き続き揮発しやすい成分を真空中で除去した。残留物をトルエンに溶解し、水で洗浄した。シリカゲル上のクロマトグラフィーにより1−(4−ニトロフェニル)−2−トリメチルシリルアセチレン89%が得られた。
エチレンとのHeckカップリング
6−メトキシ−2−ブロモナフタリン50ミリモル、炭酸カリウム60ミリモルをNMP40mlに溶解し、Pd(OAc)20.001モル%およびブチルジアダマンチルホスフィン0.004モル%と混合した。混合物を20バールのエチレン圧に配置し、130℃で完全に反応するまで撹拌した。溶解していない成分を濾過し、アルカリ溶液で洗浄し、蒸留後、6−メトキシ−2−ビニルナフタリン92%が得られた。
カルボニル化反応
6−メトキシ2−ブロモナフタリン20ミリモル、トリエチルアミン30ミリモルを1−ブタノール30mlに溶解し、Pd(OAc)20.05モル%およびブチルジアダマンチルホスフィン0.1モル%と混合した。混合物を3バールのCO圧に配置し、130℃で完全に反応するまで撹拌した。溶解していない成分を濾過し、アルカリ溶液で洗浄し、蒸留後、6−メトキシ−2−ナフタリンカルボン酸ブチルエステル94%が得られた。
Claims (14)
- 遷移金属として金属パラジウム、ニッケル、白金、ロジウム、イリジ
ウム、ルテニウム、またはコバルトを使用する請求項3〜7のいずれかに記載の使用方法
。
- 遷移金属化合物としてパラジウム化合物またはニッケル化合物を使用
する請求項3〜8のいずれかに記載の使用方法。
- 接触反応のために予め製造した、請求項8または9に記載の決めら
れた遷移金属のモノホスファン錯体、ジホスファン錯体、トリホスファン錯体またはテト
ラホスファン錯体を使用する請求項3〜7のいずれかに記載の使用方法。
- リガンドを20〜200℃の温度で使用する請求項3から10まで
のいずれか1項記載の使用方法。
- 30〜180℃に温度を保つ請求項11記載の使用方法。
- 接触的に使用する場合にホスファンリガンドを遷移金属に対して過
剰で、遷移金属とリガンドの比率1:1〜1:1000で使用する請求項3から12まで
のいずれか1項記載の使用方法。
- 遷移金属とリガンドの比率が1:1〜1:100である請求項13
記載の使用方法。
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DE10037961A DE10037961A1 (de) | 2000-07-27 | 2000-07-27 | Neue Phosphanliganden, deren Herstellung und ihre Verwendung in katalytischen Reaktionen |
PCT/EP2001/008749 WO2002010178A1 (de) | 2000-07-27 | 2001-07-27 | Adamantylgruppen enthaltende phosphanliganden, deren herstellung und ihre verwendung in katalytischen reaktionen |
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EP (1) | EP1303525B1 (ja) |
JP (1) | JP5376743B2 (ja) |
AT (1) | ATE480548T1 (ja) |
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WO (1) | WO2002010178A1 (ja) |
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CN1269784C (zh) | 2002-02-19 | 2006-08-16 | 国际壳牌研究有限公司 | 制备羧酸酐的方法和所述羧酸酐作为酰化剂的用途 |
ATE552907T1 (de) * | 2002-02-19 | 2012-04-15 | Lucite Int Uk Ltd | Verfahren zur carbonylierung ethylenisch ungesättigter verbindungen und zugehöriger katalysator |
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 |
WO2005083416A1 (ja) * | 2004-02-27 | 2005-09-09 | Japan Science And Technology Agency | 質量スペクトルと略同時に吸収・発光・散乱スペクトルを分析する分析装置および分析方法、並びに、エレクトロスプレーイオン化法を用いた質量分析装置および分析方法 |
GB0411951D0 (en) | 2004-05-28 | 2004-06-30 | Lucite Int Uk Ltd | Carbonylation of ester |
CN100337750C (zh) * | 2004-09-24 | 2007-09-19 | 中国科学院化学研究所 | 一种甲醇羰基化合成乙酸的制备方法 |
DE102005014822A1 (de) * | 2005-03-30 | 2006-10-05 | Degussa Ag | Verfahren zur Herstellung aromatischer Aldehyde |
GB0516556D0 (en) | 2005-08-12 | 2005-09-21 | Lucite Int Uk Ltd | Improved catalyst system |
WO2007057640A1 (en) | 2005-11-17 | 2007-05-24 | Lucite International Uk Limited | Carbonylation of ethylenically unsaturated compounds |
GB0607494D0 (en) | 2006-04-13 | 2006-05-24 | Lucite Int Uk Ltd | Metal complexes |
EP1894938A1 (en) | 2006-08-31 | 2008-03-05 | Evonik Degussa GmbH | New cyclopentadienyl, indenyl or fluorenyl substituted phosphine compounds and their use in catalytic reactions |
GB2448562B (en) | 2006-10-24 | 2012-02-22 | Bruker Daltonik Gmbh | Top-down protein analysis in mass spectrometers with ion traps |
DE102006056208A1 (de) * | 2006-11-29 | 2008-06-05 | Saltigo Gmbh | Verfahren zur katalytischen Herstellung von aromatischen oder heteroaromatischen Nitrilen |
CN105153241B (zh) | 2006-12-02 | 2020-05-15 | 卢西特国际英国有限公司 | 羰基化配体及其在羰基化烯键式不饱和化合物中的用途 |
GB0625518D0 (en) * | 2006-12-21 | 2007-01-31 | Lucite Int Uk Ltd | Carbonylation of conjugated dienes |
DE102007060705A1 (de) * | 2007-12-17 | 2009-06-18 | Evonik Degussa Gmbh | ω-Aminocarbonsäuren oder ihre Lactame, herstellende, rekombinante Zellen |
BRPI0912255A2 (pt) * | 2008-05-27 | 2015-10-06 | Basf Se | processo para a preparação do ácido carboxílico aromático e heteroaromático, ésteres do ácido carboxílico e carboxamidas |
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 |
JP5284037B2 (ja) * | 2008-10-30 | 2013-09-11 | 保土谷化学工業株式会社 | ビスアリールアミン誘導体の製造方法 |
DE102009000592A1 (de) | 2009-02-04 | 2010-08-05 | Evonik Degussa Gmbh | Verfahren zur Herstellung von Aminogruppen tragenden, multizyklischen Ringsystemen |
US8633127B2 (en) * | 2009-03-04 | 2014-01-21 | Chevron Phillips Chemical Company Lp | Selective hydrogenation catalyst and methods of making and using same |
EP2468702B1 (en) * | 2009-08-18 | 2018-01-17 | Nippon Soda Co., Ltd. | Method for producing aryl, heteroaryl, or alkenyl-substituted unsaturated hydrocarbon |
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 |
DE102010001364B4 (de) | 2010-01-29 | 2014-10-16 | Technische Universität Chemnitz | Neue P,O-Ferrocene, deren Herstellung und Verwendung in katalytischen Reaktionen |
DE102011004465A1 (de) | 2010-09-10 | 2012-03-15 | Evonik Degussa Gmbh | Verfahren zur direkten Aminierung sekundärer Alkohole mit Ammoniak zu primären Aminen |
DE102011075162A1 (de) | 2010-12-08 | 2012-06-14 | Evonik Degussa Gmbh | Verfahren zur homogen-katalysierte, hochselektiven direkten Aminierung von primären Alkoholen mit Ammoniak zu primären Aminen bei hohem Volumenverhältnis von Flüssig- zu Gasphase und/oder hohen Drücken |
BR112013021208A2 (pt) | 2011-02-21 | 2019-09-24 | Evonik Degussa Gmbh | processo para aminação direta de álcoois com amônia para formar aminas primárias por meio de sistema catalisador xantphos |
EP2535344A1 (de) | 2011-06-17 | 2012-12-19 | Evonik Degussa GmbH | Silsesquioxan-substituierte Verbindungen, Verfahren zu deren Herstellung, deren Verwendung als Liganden für Katalysatorsysteme sowie Katalysatorsysteme |
DE102011089008B4 (de) | 2011-12-19 | 2017-08-24 | Evonik Degussa Gmbh | Verfahren zur Herstellung von Estern aus Formiaten und olefinisch ungesättigten Verbindungen |
BR102016016724B1 (pt) | 2015-07-23 | 2021-06-29 | Evonik Operations Gmbh | Compostos com base em ferroceno e catalisadores de paládio com base nestes para a alcoxicarbonilação de compostos etilenicamente insaturados |
KR20180101330A (ko) * | 2015-10-29 | 2018-09-12 | 더 트러스티스 오브 프린세톤 유니버시티 | 트리-(아다만틸)포스핀 및 이의 적용 |
DE102017213817A1 (de) | 2017-08-08 | 2019-02-14 | RUHR-UNIVERSITäT BOCHUM | Ylid-funktionalisierte Phosphane zur Verwendung in Metallkomplexen und der homogenen Katalyse |
JP6708319B1 (ja) * | 2018-08-03 | 2020-06-10 | 日産化学株式会社 | フッ化芳香族第二級アミン化合物の製造方法 |
TW202348614A (zh) * | 2022-04-05 | 2023-12-16 | 美商普羅梅勒斯有限公司 | 具有改進的成膜特性之乙烯基加成聚合物形成用鈀觸媒 |
CN115028663B (zh) * | 2022-05-11 | 2024-08-02 | 常州德能新材料有限公司 | 一种降冰片烯基亚甲基膦及其衍生物的金属配合物 |
US20240216875A1 (en) * | 2022-12-20 | 2024-07-04 | Promerus, Llc | Supported membranes by thermal and uv inititated mass polymerization |
-
2000
- 2000-07-27 DE DE10037961A patent/DE10037961A1/de not_active Ceased
-
2001
- 2001-07-27 AT AT01969546T patent/ATE480548T1/de active
- 2001-07-27 JP JP2002515907A patent/JP5376743B2/ja not_active Expired - Lifetime
- 2001-07-27 WO PCT/EP2001/008749 patent/WO2002010178A1/de active Application Filing
- 2001-07-27 EP EP01969546A patent/EP1303525B1/de not_active Expired - Lifetime
- 2001-07-27 AU AU2001289771A patent/AU2001289771A1/en not_active Abandoned
- 2001-07-27 US US10/333,860 patent/US7148176B2/en not_active Expired - Lifetime
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EP1303525B1 (de) | 2010-09-08 |
US7148176B2 (en) | 2006-12-12 |
WO2002010178A8 (de) | 2002-04-04 |
EP1303525A1 (de) | 2003-04-23 |
US20040068131A1 (en) | 2004-04-08 |
DE50115621D1 (de) | 2010-10-21 |
WO2002010178A1 (de) | 2002-02-07 |
AU2001289771A1 (en) | 2002-02-13 |
ATE480548T1 (de) | 2010-09-15 |
JP2004505091A (ja) | 2004-02-19 |
DE10037961A1 (de) | 2002-02-07 |
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