JP2016505073A - 粗製pnpnh化合物を精製するための方法 - Google Patents
粗製pnpnh化合物を精製するための方法 Download PDFInfo
- Publication number
- JP2016505073A JP2016505073A JP2015555846A JP2015555846A JP2016505073A JP 2016505073 A JP2016505073 A JP 2016505073A JP 2015555846 A JP2015555846 A JP 2015555846A JP 2015555846 A JP2015555846 A JP 2015555846A JP 2016505073 A JP2016505073 A JP 2016505073A
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- Japan
- Prior art keywords
- solvent
- pnpnh
- compound
- sodium
- butyllithium
- 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.)
- Granted
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 33
- 230000008569 process Effects 0.000 title claims abstract description 12
- 238000006263 metalation reaction Methods 0.000 claims abstract description 10
- 239000003446 ligand Substances 0.000 claims description 39
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 36
- 125000004122 cyclic group Chemical group 0.000 claims description 19
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 18
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 13
- -1 amino, trimethylsilyl Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- 125000004437 phosphorous atom Chemical group 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 150000004792 aryl magnesium halides Chemical class 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 3
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 3
- 239000012454 non-polar solvent Substances 0.000 claims description 3
- 150000002902 organometallic compounds Chemical class 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 claims description 3
- WRIKHQLVHPKCJU-UHFFFAOYSA-N sodium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([Na])[Si](C)(C)C WRIKHQLVHPKCJU-UHFFFAOYSA-N 0.000 claims description 3
- 239000012312 sodium hydride Substances 0.000 claims description 3
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 14
- 239000011651 chromium Substances 0.000 description 14
- 238000006384 oligomerization reaction Methods 0.000 description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 11
- 239000005977 Ethylene Substances 0.000 description 11
- 239000001993 wax Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000005829 trimerization reaction Methods 0.000 description 5
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 4
- 101100167062 Caenorhabditis elegans chch-3 gene Proteins 0.000 description 4
- 101150065749 Churc1 gene Proteins 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 102100038239 Protein Churchill Human genes 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000004679 31P NMR spectroscopy Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 101100074846 Caenorhabditis elegans lin-2 gene Proteins 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 101100497386 Mus musculus Cask gene Proteins 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000004791 alkyl magnesium halides Chemical class 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 229910001320 chromium hydride Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000013058 crude material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- YSMZEMQBSONIMJ-UHFFFAOYSA-M magnesium;2-methanidylpropane;chloride Chemical compound [Mg+2].[Cl-].CC(C)[CH2-] YSMZEMQBSONIMJ-UHFFFAOYSA-M 0.000 description 1
- YHNWUQFTJNJVNU-UHFFFAOYSA-N magnesium;butane;ethane Chemical compound [Mg+2].[CH2-]C.CCC[CH2-] YHNWUQFTJNJVNU-UHFFFAOYSA-N 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- WLTSEWGSVKQUDL-UHFFFAOYSA-N n-[phenyl-(propan-2-ylamino)phosphanyl]propan-2-amine Chemical compound CC(C)NP(NC(C)C)C1=CC=CC=C1 WLTSEWGSVKQUDL-UHFFFAOYSA-N 0.000 description 1
- TZJOIDXKFOTKCW-UHFFFAOYSA-N n-cyclohexylcyclohexanamine;5-[(2-methylpropan-2-yl)oxy]-5-oxo-2-(phenylmethoxycarbonylamino)pentanoic acid Chemical compound C1CCCCC1NC1CCCCC1.CC(C)(C)OC(=O)CCC(C(O)=O)NC(=O)OCC1=CC=CC=C1 TZJOIDXKFOTKCW-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000006478 transmetalation reaction Methods 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical group C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- C07F9/6581—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 nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/6587—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 nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having two phosphorus atoms as ring hetero atoms in the same ring
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/189—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
-
- 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
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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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
- C07F9/4883—Amides or esteramides thereof, e.g. RP(NR'2)2 or RP(XR')(NR''2) (X = O, S)
-
- 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
- C07F9/6581—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 nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/6584—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 nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having one phosphorus atom as ring hetero atom
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Abstract
Description
を含む。この配位子は典型的なPNPN−H−骨格を特徴とし、このクラスの化合物がその置換基の明確な性質にかかわらず、多くの場合「PNPNH−配位子」と呼ばれるのはこのためである。
R1R2P−N(R3)−P(R4)−N(R5)−H
(式中、R1、R2、R3、R4、およびR5は、ハロゲン、アミノ、トリメチルシリル、C1〜C10アルキル、置換C1〜C10アルキル、C6〜C20アリール、および置換C6〜C20アリールから独立に選択される)
の粗製PNPNH化合物、またはPNPN−H構造のPもしくはN原子の少なくとも1つが環系の構成員であり、環系がPNPNH−構造の1つもしくは複数の構成化合物から置換により形成される任意の環状誘導体を精製するための方法であって、
a)PNPNH化合物を第1の溶媒に溶解させるステップと、
b)PNPNH化合物をメタル化するステップと、
c)ステップb)で得られるメタル化化合物を単離するステップであり、好ましくは、ステップb)で得られるメタル化化合物を析出させ、メタル化化合物および溶媒を分離し、場合により、分離したメタル化化合物を溶媒で洗浄することによる、ステップと、
d)メタル化化合物を第2の溶媒中で再プロトン化するステップと、
e)場合により溶媒を除去し、場合により再プロトン化PNPNH配位子を再結晶させるステップと、
を含む、方法である。
[ビス(イソプロピルアミノ)フェニルホスフィン(NPN)の調製]
ジエチルエーテル(250ml)中のイソプロピルアミン(30ml、352mmol)の撹拌溶液へ、ジクロロフェニルホスフィン(9.63ml、71mmol、50mlのジエチルエーテル中に溶解)を0℃で30分かけて加えた。合計72時間の撹拌の後、溶液をろ過した。残渣をジエチルエーテルで洗浄し、溶媒を真空中で除去した。残った油を0.2Torr/76〜78℃で蒸留して33%(5.3g)の収率で無色液体を得た。31P{H}NMR:49.0ppm。
テトラヒドロフラン(10ml)中のNPN種(2.4g、10.7mmol)の溶液を、−40℃にてTHF(40ml)中のトリエチルアミン(6ml)およびクロロジフェニルホスフィン(2.36g,10.7mmol)の撹拌溶液へ滴加した。室温でさらに24時間撹拌した後、トリエチルアンモニウム塩をろ去し、残渣をn−ヘキサン中に溶解させ、再びろ過し、溶液を結晶化のため−30℃で維持した。収率52%(2.3g、5.6mmol)。31P{H}NMR:41.2、68.4(broad)。
Ph2PN(i−Pr)P(Ph)N(i−Pr)−H(8.70g、21.35mmol)を15mlのトルエンに溶解させた。−78℃まで冷却した後、n−ブチルリチウム(12.8ml、2.5M n−BuLi、n−ヘプタン中、32.0mmol)を溶液へ加え、橙色/黄色への急激な色変化を生じさせた。溶液を室温でさらに2時間撹拌し、無色固体が析出した。析出物をろ過し、5mlのトルエンで3回洗浄した。残った溶媒を真空中で除去して無色粉末を得た。収率:6.73g(76%)。分子量:414.39g/mol[C24H29LiN2P2]。元素分析:計算値:C 69.56%、H 7.05%、N 6.76%;測定値:C 69.25%、H 7.06%、N 6.87%。融点:187〜189℃。1H NMR(THF−d8)δ=7.50〜7.57(m,6H,aryl−H),7.20〜7.34(m,6H,aryl−H),7.02(m,2H,arom.),6.93(m,1H,aryl−H),3,70(m,1H,CHCH3),3.58(m,1H,CHCH3),1.39(d,J=6.47Hz,3H,CHCH3),1.25(d,J=6.23Hz,3H,CHCH3),1.22(d,J=6.24Hz,3H,CHCH3),1.04(d,J=6.55Hz,3H,CHCH3);13C−NMR(THF−d8):δ=143.4,142.0,134.9,133.4,132.5,131.5,129.4,128.6,128.0,127.9,127.1,125.2(arom.),54.6,54.0(CHCH3),31.0,26.7(CHCH3);31P{H}NMR(THF−d8):δ=40.6(br),100.1pp,(d,2JP−P=24.6Hz)。
粗製配位子(8.70g、21.35mmol)を15mlのトルエンに溶解させた。冷却下でn−ブチルリチウム(12.8ml、2.5M n−BuLi、n−ヘプタン中、32.0mmol)を溶液へ加え、橙色/黄色への急激な色変化を生じさせた。溶液を室温でさらに2時間撹拌し、無色固体が析出した。析出物をろ過し、5mlのトルエンで洗浄した。残渣および塩化アンモニウム(1.70g、32mmol)をトルエン中に懸濁させた。この懸濁液を10時間撹拌した。ろ過により精製済み配位子のトルエン溶液が得られ、これは触媒反応においてさらなる処理をせずに使用できる。あるいは、溶媒を真空中で除去して5.41g(62%)を得る。分子量:408.19g/mol[C24H30N2P2]。元素分析:計算値 C 70.57%、H 7.40%、N 6.86%;測定値;C 70.50%、H 7.35%、N 6.87%。また、リチウム化化合物は十分な分析結果を示す:[Ph2PN(i−Pr)P(Ph)N(i−Pr)−Li]2、分子量:414.39g/mol[C24H29LiN2P2]。元素分析:計算値 C 69.56%、H 7.05%、N 6.76%;測定値:C 69.25%、H 7.06%、N 6.87%。
標準的なエチレンオリゴマ化(1−ヘキセンへの三量化)を行い、様々な精製技術により調製された配位子を使用した。PE/ワックスの形成を測定した。結果を表1に示す。
R1R2P−N(R3)−P(R4)−N(R5)−H
(式中、R1、R2、R3、R4、およびR5は、ハロゲン、アミノ、トリメチルシリル、C1〜C10アルキル、置換C1〜C10アルキル、C6〜C20アリール、および置換C6〜C20アリールから独立に選択される)
の粗製PNPNH化合物、またはPNPN−H構造のPもしくはN原子の少なくとも1つが環系の構成員であり、環系がPNPNH−構造の1つもしくは複数の構成化合物から置換により形成される、好ましくは環系が同じPNPNH−構造の2つの構成要素から置換により形成される任意の環状誘導体を精製するための方法であって、より好ましくは、PNPNH化合物が(Ph)2P−N(i−Pr)−P(Ph)−N(i−Pr)−H、(Ph)2P−N(i−Pr)−P(Ph)−N(Ph)−H、(Ph)2P−N(i−Pr)−P(Ph)−N(tert−ブチル)−H、(Ph)2P−N(i−Pr)−P(PH)−N(CH(CH3)(PH))−Hであり、前記方法が、(a)PNPNH化合物を第1の溶媒に溶解させるステップと;b)PNPNH化合物をメタル化するステップであり、好ましくはステップb)におけるメタル化が、有機金属化合物、塩基、ナトリウム金属、またはカリウム金属、好ましくはn−ブチルリチウム、sec−ブチルリチウム、tert−ブチルリチウム、シクロペンタジエニルナトリウム、水素化ナトリウム、ナトリウムアミド、アルキルまたはアリールマグネシウムハロゲン化物、ナトリウムビス(トリメチルシリル)アミド、ジアルキルマグネシウム、ジアリールマグネシウム、トリアルキルアルミニウム、ジアルキル亜鉛、ナトリウムまたはカリウム金属、最も好ましくはn−ブチルリチウムを、PNPNH配位子のモル濃度と等しいまたはそれを超える量で、ステップa)で得られる溶液中に加え、好ましくはステップb)で得られるメタル化化合物を析出させることによりステップb)で得られるメタル化化合物を単離し、溶媒から分離し、場合により溶媒で洗浄することによる、ステップと;(c)メタル化化合物を第2の溶媒中で再プロトン化するステップであり、好ましくはステップc)における再プロトン化が酸、好ましくは弱酸、最も好ましくはハロゲン化アンモニウム、好ましくは塩化アンモニウム、リン酸、硫化水素、またはホウ酸を添加することにより実現される、ステップと、(d)場合により溶媒を除去し、場合により再プロトン化PNPNH配位子を再結晶させるステップであり、好ましくは第1および第2の溶媒が同一であり、無極性溶媒であり、好ましくは芳香族および/または脂肪族の溶媒、好ましくはトルエン、n−ヘキサン、シクロヘキサン、1−ヘキセン、または前述のものを少なくとも1つ含む組み合わせである、ステップとを含む、方法である。
Claims (7)
- 一般構造
R1R2P−N(R3)−P(R4)−N(R5)−H
(式中、R1、R2、R3、R4、およびR5は独立に、ハロゲン、アミノ、トリメチルシリル、C1〜C10アルキル、置換C1〜C10アルキル、C6〜C20アリール、および置換C6〜C20アリールである)
の粗製PNPNH化合物、またはPNPN−H構造のPもしくはN原子の少なくとも1つが環系の構成員であり、前記環系がPNPNH−構造の1つもしくは複数の構成化合物から置換により形成される任意の環状誘導体を精製するための方法であって、
a)前記PNPNH化合物を第1の溶媒に溶解させるステップと、
b)前記PNPNH化合物をメタル化するステップと、
c)ステップb)で得られるメタル化化合物を単離するステップであり、好ましくは、ステップb)で得られる前記メタル化化合物を析出させ、前記溶媒から分離し、場合により前記溶媒で洗浄することによる、ステップと、
d)前記メタル化化合物を第2の溶媒中で再プロトン化するステップと、
e)場合によりその溶媒を除去し、場合により前記再プロトン化されたPNPNH配位子を再結晶させるステップと、
を含むことを特徴とする、方法。 - 請求項1に記載の方法であって、前記第1の溶媒および前記第2の溶媒が同一であることを特徴とする方法。
- 請求項1に記載の方法であって、前記第1の溶媒および/または前記第2の溶媒が、無極性溶媒、好ましくは芳香族および/または脂肪族の溶媒、好ましくはトルエン、n−ヘキサン、シクロヘキサン、1−ヘキセン、または前述のものを少なくとも1つ含む組み合わせであることを特徴とする方法。
- 請求項1から3のいずれか一項に記載の方法であって、ステップb)におけるメタル化が、有機金属化合物、塩基、ナトリウム金属、またはカリウム金属を、前記PNPNH配位子のモル濃度と等しいかまたはそれを超える量で、ステップa)で得られる溶液へ加えることによることを特徴とする方法。
- 請求項4に記載の方法であって、前記メタル化が、n−ブチルリチウム、sec−ブチルリチウム、tert−ブチルリチウム、シクロペンタジエニルナトリウム、水素化ナトリウム、ナトリウムアミド、アルキルもしくはアリールマグネシウムハロゲン化物、ナトリウムビス(トリメチルシリル)アミド、ジアルキルマグネシウム、ジアリールマグネシウム、トリアルキルアルミニウム、ジアルキル亜鉛、ナトリウム金属、またはカリウム金属、好ましくはn−ブチルリチウムを加えることによることを特徴とする方法。
- 請求項1から5のいずれか一項に記載の方法であって、ステップd)における再プロトン化が、酸、好ましくは弱酸を加えることにより実現されることを特徴とする方法。
- 請求項6に記載の方法であって、前記酸が、ハロゲン化アンモニウム、好ましくは塩化アンモニウム、リン酸、硫化水素、またはホウ酸であることを特徴とする方法。
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