WO2015011139A2 - Phosphoramiditderivate in der hydroformylierung von olefinhaltigen gemischen - Google Patents
Phosphoramiditderivate in der hydroformylierung von olefinhaltigen gemischen Download PDFInfo
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- WO2015011139A2 WO2015011139A2 PCT/EP2014/065722 EP2014065722W WO2015011139A2 WO 2015011139 A2 WO2015011139 A2 WO 2015011139A2 EP 2014065722 W EP2014065722 W EP 2014065722W WO 2015011139 A2 WO2015011139 A2 WO 2015011139A2
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- WIPO (PCT)
- Prior art keywords
- substituted
- radicals
- alkyl
- transition metal
- unsubstituted
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 67
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 30
- 150000008300 phosphoramidites Chemical class 0.000 title claims abstract description 26
- 150000001336 alkenes Chemical class 0.000 title claims description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 62
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 35
- 150000003624 transition metals Chemical class 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 32
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011541 reaction mixture Substances 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims abstract description 10
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- -1 aromatic radical Chemical class 0.000 claims description 55
- 150000005840 aryl radicals Chemical class 0.000 claims description 34
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 33
- 239000003446 ligand Substances 0.000 claims description 31
- 125000000623 heterocyclic group Chemical group 0.000 claims description 26
- 229930195733 hydrocarbon Natural products 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000004215 Carbon black (E152) Substances 0.000 claims description 17
- 239000010948 rhodium Substances 0.000 claims description 17
- 239000004305 biphenyl Substances 0.000 claims description 15
- 125000002947 alkylene group Chemical group 0.000 claims description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 229910052703 rhodium Inorganic materials 0.000 claims description 11
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical group [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 11
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalene Chemical group C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000005336 cracking Methods 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 238000006384 oligomerization reaction Methods 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 238000004230 steam cracking Methods 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 239000007857 degradation product Substances 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 238000005481 NMR spectroscopy Methods 0.000 description 22
- 239000000047 product Substances 0.000 description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 11
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical class CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 7
- 0 Cc1cc(C)c2O*(*3CCCCC3)Oc(c(**)cc(C)c3)c3-c2c1 Chemical compound Cc1cc(C)c2O*(*3CCCCC3)Oc(c(**)cc(C)c3)c3-c2c1 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000005882 aldol condensation reaction Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- POILWHVDKZOXJZ-ONEGZZNKSA-M (E)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C/C(C)=O POILWHVDKZOXJZ-ONEGZZNKSA-M 0.000 description 2
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 2
- UPSVYNDQEVZTMB-UHFFFAOYSA-N 2-methyl-1,3,5-trinitrobenzene;1,3,5,7-tetranitro-1,3,5,7-tetrazocane Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O.[O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 UPSVYNDQEVZTMB-UHFFFAOYSA-N 0.000 description 2
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 102100023477 Transcription cofactor vestigial-like protein 2 Human genes 0.000 description 2
- 101710176144 Transcription cofactor vestigial-like protein 2 Proteins 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 description 2
- DQTRYXANLKJLPK-UHFFFAOYSA-N chlorophosphonous acid Chemical compound OP(O)Cl DQTRYXANLKJLPK-UHFFFAOYSA-N 0.000 description 2
- WQABCVAJNWAXTE-UHFFFAOYSA-N dimercaprol Chemical compound OCC(S)CS WQABCVAJNWAXTE-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- BUYVJWVYKPKZEX-DWVXZKBMSA-N (1z,5z)-cycloocta-1,5-diene;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].C\C(O)=C\C(C)=O.C\1C\C=C/CC\C=C/1 BUYVJWVYKPKZEX-DWVXZKBMSA-N 0.000 description 1
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 1
- ILPBINAXDRFYPL-HWKANZROSA-N (E)-2-octene Chemical compound CCCCC\C=C\C ILPBINAXDRFYPL-HWKANZROSA-N 0.000 description 1
- YCTDZYMMFQCTEO-FNORWQNLSA-N (E)-3-octene Chemical compound CCCC\C=C\CC YCTDZYMMFQCTEO-FNORWQNLSA-N 0.000 description 1
- CTQNGGLPUBDAKN-ZGYYUIRESA-N 1,2,3,4-tetradeuterio-5,6-bis(trideuteriomethyl)benzene Chemical compound [2H]C1=C([2H])C([2H])=C(C([2H])([2H])[2H])C(C([2H])([2H])[2H])=C1[2H] CTQNGGLPUBDAKN-ZGYYUIRESA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CAPAOPVDGQSWAM-UHFFFAOYSA-N 1h-pyrrol-2-ylphosphane Chemical class PC1=CC=CN1 CAPAOPVDGQSWAM-UHFFFAOYSA-N 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- 238000004639 Schlenk technique Methods 0.000 description 1
- 102100023478 Transcription cofactor vestigial-like protein 1 Human genes 0.000 description 1
- 101710176146 Transcription cofactor vestigial-like protein 1 Proteins 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000005669 hydrocyanation reaction Methods 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000003041 laboratory chemical Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- SXADIBFZNXBEGI-UHFFFAOYSA-N phosphoramidous acid Chemical group NP(O)O SXADIBFZNXBEGI-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
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- 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
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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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
- C07F9/657154—Cyclic esteramides of oxyacids of phosphorus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
- B01J31/186—Mono- or diamide derivatives thereof
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- 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
- B01J31/20—Carbonyls
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- 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
-
- C—CHEMISTRY; METALLURGY
- 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
- C07C45/505—Asymmetric hydroformylation
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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
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- 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
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/001—General concepts, e.g. reviews, relating to catalyst systems and methods of making them, the concept being defined by a common material or method/theory
- B01J2531/002—Materials
- B01J2531/004—Ligands
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
- B01J2531/821—Ruthenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
- B01J2531/822—Rhodium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
- B01J2531/827—Iridium
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- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
Definitions
- Hydroformylation is one of the quantitatively most important homogeneous catalysis on an industrial scale.
- the aldehydes produced therewith are important intermediate or end products in the chemical industry (Rhodium Catalyzed Hydroformylation, PWNM van Leeuwen, C. Claver, ed., Klüver Academic Publishers: Dordrecht Netherlands, 2000. R. Franke, D. Selent, A. Börner, Chem. Rev. 2012, 112, 5675). Of particular importance is the hydroformylation with Rh catalysts.
- Phosphoramidites i. Compounds that possess one or more P-N bonds instead of P-O have rarely been used as ligands in hydroformylation.
- Van Leeuwen and co-workers (A. van Rooy, D. Burgers, PCJ Kamer, PWNM van Leeuwen, Recl. Trav. Chim. Pays-Bas 1996, 115, 492) first studied monodentate phosphoramidites in hydroformylation. Overall, only moderate catalytic properties were observed at the high to extremely high ligand / rhodium ratios of up to 1000: 1. At the lowest ligand / rhodium or P / Rh ratio of 10: 1, a high isomerization activity and the formation of internal Olefins found that are not hydroformylated. Only increasing the P / Rh ratio increased the TOF to a moderate 910 h "1 and increased the selectivity.
- phosphoramidites are more likely to react with nucleophiles than phosphites. This property is e.g. widely used for the synthesis of phosphites from phosphoramidites (e-EROS Encyclopedia of Reagents for Organic Synthesis, doi: 10.1002 / 047084289X.rn00312; R. Hülst, NK de Vries, BL Feringa, Tetrahedron: Asymmetry 1994, 5, 699-708) , but at the same time it is particularly questioning its suitability as a long-term stable ligand for catalysis.
- P-substituents For the stabilization of hydrolysis-prone phosphorus compounds, the use of suitable P-substituents may contribute.
- the only hitherto described method in the context of phosphoramidite ligands is the use of N-pyrrolyl radicals on the phosphorus (WO 02/083695).
- Substituents on the heterocycle such as e.g. 2-ethylpyrrolyl (WO 03018192, DE 102005061642) or indolyl (WO 03/018192) further improve the hydrolytic stability.
- hydrolytic degradation of phosphoramidite ligands can also be slowed by the addition of amines to the hydroformylation reaction, as taught in EP 167791 1, US 2006/0224000 and US 8,110,709.
- the use of hydrolysis-stable pyrrolylphosphines or the addition of basic stabilizers narrows the scope of the hydroformylation reaction strongly to these embodiments.
- the object of the present invention is to provide hydrolysis-stable ligands for catalytically active compositions for the chemical synthesis of organic compounds, in particular hydroformylation, hydrocyanation and the hydrogenation of unsaturated compounds.
- hydrolysis-stable ligands for catalytically active compositions for the chemical synthesis of organic compounds, in particular hydroformylation, hydrocyanation and the hydrogenation of unsaturated compounds.
- An object of the present invention are phosphoramidites of the formula (I), wherein Q is a bivalent substituted or unsubstituted aromatic radical; wherein R 1 is selected from alkyl, substituted or unsubstituted cycloalkyl or aryl radicals;
- R 2 is selected from alkyl, substituted or unsubstituted cycloalkyl or aryl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure with N.
- Q is selected from substituted or unsubstituted 1, ⁇ -biphenyl, 1, 1 ' -binaphthyl or ortho-phenyl radicals, in particular substituted or unsubstituted 1, ⁇ -biphenyl radicals.
- R 1 is selected from C 1 -C 5 -alkyl, substituted or unsubstituted cycloalkyl or aryl radicals
- R 2 is selected from C 1 -C 5 alkyl, substituted or unsubstituted cycloalkyl or aryl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure via alkylene groups with N.
- R 1 is selected from C 1 -C 5 -alkyl, C 4 -C 6 -cycloalkyl or phenyl radicals
- R 2 is selected from C 1 -C 5 -alkyl, C 4 -C 6 -cycloalkyl or phenyl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure via alkylene groups with N.
- the compounds of the formula (I) are selected from:
- transition metal-containing compounds of the formula Me (acac) (CO) L with Me transition metal, wherein L is selected from: wherein Q is a divalent substituted or unsubstituted aromatic radical;
- R 1 is selected from alkyl, substituted or unsubstituted cycloalkyl or aryl radicals
- R 2 is selected from alkyl, substituted or unsubstituted cycloalkyl or aryl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure with N.
- Q is selected from substituted or unsubstituted 1, ⁇ -biphenyl, 1, 1 ' -binaphthyl or ortho-phenyl radicals, in particular substituted or unsubstituted 1, ⁇ -Biphenylresten.ln a variant of this Ausry- R 1 form is selected from d- - C 5 -alkyl, substituted or unsubstituted
- R 2 is selected from C 1 -C 5 -alkyl, substituted or unsubstituted cycloalkyl or aryl radicals, but R 1 and R 2 are not i-propyl radicals, or
- R 1 and R 2 form a heterocyclic structure via alkylene groups with N.
- R 1 is selected from C 1 -C 5 -alkyl
- R 2 is selected from C 1 -C 5 -alkyl-, C 4 -C 6-
- R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure via alkylene groups with N.
- the compounds of the formula (I) are selected from:
- salts such as halides, carboxylates - e.g. Acetates - or commercially available complex compounds, such.
- Q is a divalent substituted or unsubstituted aromatic radical
- R 1 is selected from alkyl, substituted or unsubstituted cycloalkyl or aryl radicals
- R 2 is selected from alkyl, substituted or unsubstituted cycloalkyl or aryl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure with N.
- Q is a divalent substituted or unsubstituted aromatic radical
- R 1 is selected from alkyl, substituted or unsubstituted cycloalkyl or aryl radicals
- R 2 is selected from alkyl, substituted or unsubstituted cycloalkyl or aryl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure with N.
- solvents are understood to mean, in addition to substances which do not inhibit product formation-externally added to the reaction mixture or submitted to it-also mixtures of compounds which are formed in situ from secondary or subsequent reactions of the products; For example, so-called high boilers that arise from the aldol condensation, the acetalization of the primary product aldehydes as well as the esterification and lead to the corresponding aldol products, formates, acetals and ethers.
- Solvents initially introduced into the reaction mixture can be aromatics, such as, for example, toluene-rich aromatic mixtures or alkanes or mixtures of alkanes.
- high boilers are understood as meaning those substances or else mixtures of substances which boil aldehydes at a higher temperature than the primary product and have higher molar masses than the primary product aldehydes.
- the structural element Q - in the transition metal-containing compounds as well as the free ligand - is selected from substituted or unsubstituted 1, ⁇ -biphenyl, 1, 1 '-Binaphthyl- or ortho- Phenyl radicals, in particular substituted or unsubstituted 1, ⁇ -biphenyl radicals.
- R 1 is selected from C 1 -C 5 -alkyl, substituted or unsubstituted cycloalkyl or aryl radicals
- R 2 is selected from C 1 to C 5 alkyl, substituted or unsubstituted cycloalkyl or aryl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure via alkylene groups with N ,
- R 1 is selected from C 1 -C 5 -alkyl, C 4 -C -cycloalkyl or phenyl radicals
- R 2 is selected from C 1 -C 5 alkyl, C 4 -C 8 cycloalkyl or phenyl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic via N-alkylene groups Structure.
- transition metal-containing compounds of the formula Me (acac) (CO) L with Me transition metal, where L is selected from:
- the free ligands are selected under:
- the unsaturated compounds which are hydroformylated in the process of the invention include hydrocarbon mixtures obtained in petrochemical processing plants. These include, for example, so-called C 4 - Thomaste. Typical compositions of C 4 cuts from which most of the polyunsaturated hydrocarbons have been removed and which can be used in the process according to the invention are listed in the following Table 1 (see DE 10 2008 002188). Table 1 :
- HCC 4 typical of a C 4 mixture obtained from the C 4 cut of a high-severity steam after the hydrogenation of the 1,3-butadiene without additional moderation of the catalyst.
- HCC 4 / SHP composition HCC 4 in which residues of 1, 3-butadiene in one
- CC 4 / SHP composition of a C 4 cut in which residues of 1,3-butadiene were further reduced in a selective hydrogenation process / SHP.
- the unsaturated compound or its mixture is selected from:
- Hydrocarbon mixtures from catalytically operated splitting plants such as e.g. FCC cracking plants;
- Hydrocarbon mixtures from oligomerization processes in homogeneous phase and heterogeneous phases such as the OCTOL, DIMERSOL, Fischer-Tropsch, Polygas, CatPoly, InAlk, Polynaphtha, Selectopol, MOGD, COD, EMOGAS, NExOCTANE or SHOP process;
- Hydrocarbon mixtures comprising polyunsaturated compounds.
- the mixture comprises unsaturated compounds having 2 to 30 carbon atoms.
- the mixture comprises unsaturated compounds having 2 to 8 carbon atoms.
- the mixture has polyunsaturated hydrocarbons.
- the mixture comprises butadienes.
- n-octenes, 1-octene and Cs-containing olefin mixtures are hydroformylated as olefin-containing mixtures.
- phosphoramidites of the formulas (I) are prepared in a first process step:
- Q is a divalent substituted or unsubstituted aromatic radical
- R 1 is selected from alkyl, substituted or unsubstituted cycloalkyl or aryl radicals
- R 2 is selected from alkyl, substituted or unsubstituted cycloalkyl or Aryl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure with N;
- Q is selected from substituted or unsubstituted 1, ⁇ -biphenyl, 1, 1 ' -binaphthyl or ortho-phenyl radicals, in particular substituted or unsubstituted 1, ⁇ -biphenyl radicals;
- R 1 is selected from C 1 to C 5 alkyl, substituted or unsubstituted cycloalkyl or aryl radicals
- R 2 is selected from the group consisting of - C 5 - alkyl, substituted or unsubstituted cycloalkyl or aryl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure via alkylene groups with N;
- R 1 is selected from C 1 -C 5 -alkyl, C 4 -C -hydroxyalkyl or phenyl radicals
- R 2 is selected from C 1 -C 5 alkyl, C 4 -C 6 cycloalkyl or phenyl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form heterocyclic via alkylene groups with N Structure;
- R 1 is selected from alkyl, substituted or unsubstituted cycloalkyl or aryl radicals
- R 2 is selected from alkyl, substituted or unsubstituted cycloalkyl or aryl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure with N;
- Q is selected from substituted or unsubstituted 1, ⁇ -biphenyl, 1, 1 ' -binaphthyl or ortho-phenyl radicals, in particular substituted or unsubstituted 1, ⁇ -biphenyl radicals;
- R 1 is selected from C 1 to C 5 alkyl, substituted or unsubstituted cycloalkyl or aryl radicals
- R 2 is selected from the group consisting of - C 5 - alkyl, substituted or unsubstituted cycloalkyl or aryl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure via alkylene groups with N;
- R 1 is selected from C 1 -C 5 -alkyl, C 4 -C 6 -cycloalkyl or phenyl radicals
- R 2 is selected from C 1 -C 5 alkyl, C 4 -C 6 cycloalkyl or phenyl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure via alkylene groups with N;
- Q is a divalent substituted or unsubstituted aromatic radical
- R 1 is selected from alkyl, substituted or unsubstituted Cydoalkyl- or aryl radicals
- R 2 is selected from alkyl, substituted or unsubstituted cycloalkyl or aryl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure with N;
- Q is selected from substituted or unsubstituted 1, ⁇ -biphenyl, 1, 1 ' -binaphthyl or ortho-phenyl radicals, in particular substituted or unsubstituted 1, ⁇ -biphenyl radicals;
- R 1 is selected from C 1 to C 5 alkyl, substituted or unsubstituted cycloalkyl or aryl radicals
- R 2 is selected from the group consisting of - C 5 - alkyl, substituted or unsubstituted cycloalkyl or aryl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure via alkylene groups with N;
- R 1 is selected from C 1 -C 5 -alkyl, C 4 -C 6 -cycloalkyl or phenyl radicals
- R 2 is selected from C 1 -C 5 alkyl, C 4 -C 6 cycloalkyl or phenyl radicals, but R 1 and R 2 are not i-propyl radicals, or R 1 and R 2 form a heterocyclic structure via alkylene groups with N;
- the unsaturated compounds are added to form a multi-phase reaction mixture
- the reaction mixture is separated into aldehydes, alcohols, high boilers, ligands, degradation products of the catalytically active composition.
- the addition of the unsaturated compounds takes place together with that of the precursor of the transition metal and of the ligands; This is preferably when the unsaturated compounds are present at room temperature and atmospheric pressure corresponding to 1013 hPa in a liquid state.
- decomposition products are understood to mean substances which originate from the decomposition of the composition catalytically active in the hydroformylation. They are disclosed, for example, in US 5364950, US 5763677, as well as in Catalyst Separation, Recovery and Recycling, edited by DJ Cole-Hamilton, RP Tooze, 2006, NL, pages 25-26, and in rhodium-catalyzed hydroformylation, ed. by PWNM van Leeuwen et C. Claver, Kluwer Academic Publishers 2006, AA Dordrecht, NL, page 206-21.
- the final subject of the present invention is a multiphase reaction mixture containing: - unsaturated compounds
- transition metal Me is selected from ruthenium, cobalt, rhodium, iridium, in particular rhodium;
- unsaturated compounds are selected from:
- Hydrocarbon mixtures from catalytically operated splitting plants such as e.g. FCC cracking plants;
- Hydrocarbon mixtures from oligomerization processes in homogeneous phase and heterogeneous phases such as the OCTOL, DIMERSOL, Fischer-Tropsch, Polygas, CatPoly, InAlk, Polynaphtha, Selectopol, MOGD, COD, EMOGAS, NExOCTANE or SHOP process;
- Hydrocarbon mixtures comprising polyunsaturated compounds; wherein the solvent is added externally and does not interfere with the hydroformylation reaction, in particular if the solvent is formed in-situ from the primary products.
- Nuclear resonance spectra were recorded on Bruker Avance 300 and Bruker Avance 400, gas chromatographic analysis on Agilent GC 7890A, elemental analysis on Leco TruSpec CHNS and Varian ICP-OES 715, and ESI-TOF mass spectrometry on Thermo Electron Finnigan MAT 95 XP and Agilent 6890 N / 5973 devices.
- the hydroformylation was carried out in a 200 ml autoclave equipped with pressure maintenance, gas flow measurement, gassing stirrer and pressure pipette as the reaction zone.
- the toluene used as the solvent was treated with sodium ketyl and distilled under argon.
- the mixture of the n-octenes used as substrate was refluxed for several hours over sodium and distilled under argon.
- the transition metal was used as a precursor in the form of
- reaction was conducted at constant pressure. After the reaction time, the autoclave was cooled to room temperature, expanded with stirring and purged with argon. Each 1 ml of the reaction mixtures was taken immediately after switching off the stirrer, diluted with 5 ml of pentane and analyzed by gas chromatography.
- the relative activities are determined by the ratio of k 1-order to k0, i. the k value at time 0 of the reaction (reaction start) determines and describes the relative decrease in activity during the experimental period.
- the k-values of the I order are obtained from a plot of (-ln (1-gain)) versus time.
- the hydroformylation series of Tables 1 and 2 disclose that the phosphoramidites (1 a) to (1 d) according to the invention have at least comparable results in terms of catalytic activity - measured as k 0 bs. [min "1] -.. and having the yield and selectivity of n-ligands for comparison Alkanox ® 240 according to CAS Reg No. [93347- 72-9], [31570-04-4], sometimes even in these individual features superior to the comparison ligand are.
- the ligands (1 a) and (1d) according to the invention thus fulfill the stated object due to their particular hydrolytic stability, as already explained above.
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Abstract
Description
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US14/906,696 US20170014816A1 (en) | 2013-07-23 | 2014-07-22 | Phosphoramidite derivatives in the hydroformylation of olefin-containing mixtures |
EP14741637.4A EP3024838A2 (de) | 2013-07-23 | 2014-07-22 | Phosphoramiditderivate in der hydroformylierung von olefinhaltigen gemischen |
SG11201600386UA SG11201600386UA (en) | 2013-07-23 | 2014-07-22 | Phosphoramidite derivatives in the hydroformylation of olefin-containing mixtures |
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DE102013214378.8A DE102013214378A1 (de) | 2013-07-23 | 2013-07-23 | Phosphoramiditderivate in der Hydroformylierung von olefinhaltigen Gemischen |
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AU2003219901A1 (en) * | 2003-02-27 | 2004-09-28 | Mitsubishi Chemical Corporation | Optically active phosphites and phosphoramides bearing biphenol skeletons with axial chirality, and their use in catalytic asymmetric reactions |
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WO2015011139A4 (de) | 2015-05-07 |
DE102013214378A1 (de) | 2015-01-29 |
EP3024838A2 (de) | 2016-06-01 |
WO2015011139A3 (de) | 2015-03-19 |
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