EP3024839A1 - Phosphoramiditderivate in der hydroformylierung von ungesättigten verbindungen - Google Patents
Phosphoramiditderivate in der hydroformylierung von ungesättigten verbindungenInfo
- Publication number
- EP3024839A1 EP3024839A1 EP14744048.1A EP14744048A EP3024839A1 EP 3024839 A1 EP3024839 A1 EP 3024839A1 EP 14744048 A EP14744048 A EP 14744048A EP 3024839 A1 EP3024839 A1 EP 3024839A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- substituted
- transition metal
- unsubstituted
- formula
- hydroformylation
- 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.)
- Withdrawn
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 56
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 32
- 150000008300 phosphoramidites Chemical class 0.000 title claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 47
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 31
- 150000003624 transition metals Chemical class 0.000 claims abstract description 30
- 239000010948 rhodium Substances 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 15
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 14
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 11
- 239000011541 reaction mixture Substances 0.000 claims abstract description 11
- 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
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 6
- 239000010941 cobalt Substances 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract 3
- 239000003446 ligand Substances 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 229930195733 hydrocarbon Natural products 0.000 claims description 20
- 239000004305 biphenyl Substances 0.000 claims description 19
- 239000004215 Carbon black (E152) Substances 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 150000002430 hydrocarbons Chemical class 0.000 claims description 17
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 14
- 150000001336 alkenes Chemical class 0.000 claims description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000005336 cracking Methods 0.000 claims description 4
- 238000006384 oligomerization reaction Methods 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
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 abstract 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 abstract 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- -1 2-ethylpyrrolyl Chemical group 0.000 description 32
- 238000005481 NMR spectroscopy Methods 0.000 description 23
- IIVWHGMLFGNMOW-UHFFFAOYSA-N 2-methylpropane Chemical compound C[C](C)C IIVWHGMLFGNMOW-UHFFFAOYSA-N 0.000 description 22
- 239000000047 product Substances 0.000 description 18
- 150000004702 methyl esters Chemical class 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical class CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-UHFFFAOYSA-N 0.000 description 3
- FSHNFAOXXJLGJE-UHFFFAOYSA-N [Rh].[P] Chemical compound [Rh].[P] FSHNFAOXXJLGJE-UHFFFAOYSA-N 0.000 description 3
- 238000005882 aldol condensation reaction Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 238000004817 gas chromatography Methods 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
- 239000011734 sodium Substances 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
- 239000002028 Biomass Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 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
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 229940073769 methyl oleate Drugs 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
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- WPWHSFAFEBZWBB-UHFFFAOYSA-N 1-butyl radical Chemical compound [CH2]CCC WPWHSFAFEBZWBB-UHFFFAOYSA-N 0.000 description 1
- 125000001462 1-pyrrolyl group Chemical group [*]N1C([H])=C([H])C([H])=C1[H] 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
- 241000283891 Kobus Species 0.000 description 1
- 241001328813 Methles Species 0.000 description 1
- 238000004639 Schlenk technique Methods 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
- 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
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000010779 crude oil Substances 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
- ZQPPMHVWECSIRJ-MDZDMXLPSA-M elaidate Chemical compound CCCCCCCC\C=C\CCCCCCCC([O-])=O ZQPPMHVWECSIRJ-MDZDMXLPSA-M 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
- GZNGXBKEQQDPJJ-UHFFFAOYSA-N formyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=O GZNGXBKEQQDPJJ-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 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
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis 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
- 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
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- KNYPPUDDPVSAQF-UHFFFAOYSA-N methyl 2-formyloctadecanoate Chemical compound CCCCCCCCCCCCCCCCC(C=O)C(=O)OC KNYPPUDDPVSAQF-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- IKIGNQHSDISMLY-UHFFFAOYSA-N methyl octadecanoate;2-methyloctadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC.CCCCCCCCCCCCCCCCC(C)C(O)=O IKIGNQHSDISMLY-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 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
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011002 quantification 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
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000010517 secondary reaction Methods 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
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/06—Formation or introduction of functional groups containing oxygen of carbonyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
-
- 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
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0073—Rhodium compounds
-
- 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
- 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
-
- 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
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
-
- 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
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
-
- 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
- B01J2531/82—Metals of the platinum group
- B01J2531/827—Iridium
-
- 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 were observed, which were not hydroformylated.
- 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 questions their suitability as long-term stable ligands for catalysis. For example, it is known to use phosphoramidites as stabilizers for polyolefins, as disclosed in EP 0005500 A1.
- P-substituents may contribute to the stabilization of hydrolysis-prone phosphorus compounds.
- the only phosphoramidite ligand method described so far is the use of N-pyrrolyl residues on the 201300234
- 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.
- 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 ligands for catalytically active compositions for the chemical synthesis of organic compounds, in particular hydroformylation, hydrocyanation and the hydrogenation of unsaturated compounds, which have maximum or improved catalytic activity, measured as activity k 0 bs . [min "1 ], even at significantly lower phosphorus - rhodium concentration ratios - short P / Rh ratio - compared to the previously described in the prior art ligands. This is particularly relevant for use in large-scale processes, as a higher activity aldehydes in the reaction zone, thus reducing yield-reducing secondary reactions of the target products, eg aldolization reactions, and optimizing the overall economic efficiency of the large-scale process be achieved. 201300234
- R 1 is hydrogen and R 2 is C 1 -C 10 -, preferably C 1 -C 5 -alkyl, substituted or unsubstituted C 4 -C 6 -cycloalkyl or phenyl radicals, and where no R 2 is tert-butyl radical.
- Preferred substituted 1, ⁇ -biphenyl radicals are those which in the 3,3 ' and / or 5,5 ' - position of the 1, 1 ' biphenyl-2,2 ' -diolgrund stressess an alkyl radical, preferably a C 1 -C 4 -alkyl radical and particularly preferably have a tert-butyl radical (t-Bu).
- Preferred radicals for R 2 are unbranched and / or branched C 1 -C 5 -alkyl, substituted or unsubstituted C 4 -C 6 -cycloalkyl, phenyl radicals with the exception of one tert-butyl radical (t-Bu).
- Q is selected from substituted or unsubstituted ⁇ , ⁇ -biphenyl radicals
- R 1 is hydrogen and R 2 is C 1 -C 10 -, preferably C 1 -C 5 -alkyl, substituted or unsubstituted C 4 -C 6 -cycloalkyl or phenyl radicals, wherein R 2 is not a tert-butyl radical
- the transition metal Me is selected from ruthenium, cobalt, rhodium, iridium, with rhodium being particularly preferred.
- Preferred substituted 1, ⁇ -biphenyl radicals are those which in the 3,3 ' and / or 5,5 ' - position of the 1, 1 ' biphenyl-2,2 ' -diolgrund stressess an alkyl radical, preferably a C 1 -C 4 -alkyl radical and particularly preferably have a tert-butyl radical (t-Bu).
- Preferred radicals for R 2 are unbranched and / or branched C 1 -C 5 -alkyl, substituted or unsubstituted C 4 -C 6 -cycloalkyl, phenyl radicals with the exception of one tert-butyl radical (t-Bu).
- L is selected from: 201300234
- the transition metal can be used as a precursor in the form of its salts, such as the halides, carboxylates - eg acetates - or commercially available complex compounds, such as.
- This reaction can be carried out in an upstream reaction as well as in the presence of a hydrogen and carbon monoxide-containing gas mixture.
- Another object of the present invention are catalytically active compositions in the hydroformylation comprising:
- R 1 is hydrogen and R 2 is C 1 -C 10 -alkyl, preferably C 1 -C 5 -alkyl, substituted or unsubstituted C 4 -C 6 -cycloalkyl or phenyl radicals, where R 2 is not a tert-butyl radical , and wherein the transition metal Me is selected from ruthenium, cobalt, rhodium, iridium, and preferably rhodium.
- Preferred substituted 1, ⁇ -biphenyl radicals are those which in the 3,3 ' and / or 5,5 ' - position of the 1, 1 ' biphenyl-2,2 ' -diolgrund stressess an alkyl radical, preferably a C 1 -C 4 -alkyl radical and particularly preferably have a tert-butyl radical (t-Bu);
- R 2 preferred radicals for R 2 are unbranched and / or branched C 1 -C 5 -alkyl, substituted or unsubstituted C 4 -C 6 -cycloalkyl, phenyl radicals with the exception of one tert-butyl radical (t-Bu);
- L is selected from:
- Q is selected from substituted or unsubstituted ⁇ , ⁇ -biphenyl radicals
- R 1 is hydrogen and R 2 is C 1 -C 10 -alkyl, preferably C 1 -C 5 -alkyl, substituted or unsubstituted C 4 -C 6 -cycloalkyl or phenyl radicals wherein R 2 is not a tert-butyl radical.
- Preferred substituted 1, ⁇ -biphenyl radicals are those which in the 3,3 ' and / or 5,5 ' - position of the 1, 1 ' biphenyl-2,2 ' -diolgrund stressess an alkyl radical, preferably a C 1 -C 4 -alkyl radical and particularly preferably have a tert-butyl radical (t-Bu);
- R 2 preferred radicals for R 2 are unbranched and / or branched C 1 -C 5 -alkyl, substituted or unsubstituted C 4 -C 6 -cycloalkyl, phenyl radicals with the exception of one tert-butyl radical (t-Bu);
- preferred free ligands of formula (I) are selected from:
- 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 externally added to the reaction mixture may contain aromatics, e.g. 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.
- Hydrocarbon niches comprising polyunsaturated compounds
- the unsaturated compounds which are hydroformylated in the process according to the invention preferably comprise hydrocarbon mixtures which are obtained in petrochemical processing plants. These may include, for example, so-called io C 4 cuts. Typical compositions of C 4 cuts, from which preferably 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).
- HCC 4 typical of a C 4 mixture obtained from the C 4 cut of a high severity steamer after the hydrogenation of the 1,3-butadiene without additional
- HCC 4 / SHP composition HCC 4 in which residues of 1, 3-butadiene in one
- 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; unsaturated carboxylic acid derivatives.
- the unsaturated compounds or mixtures thereof used in the process according to the invention preferably have unsaturated compounds having 2 to 30 carbon atoms, more preferably having 2 to 8 carbon atoms.
- polyunsaturated hydrocarbons or mixtures containing them are used in the process according to the invention, the polyunsaturated hydrocarbons are preferably butadienes. 201300234
- unsaturated carboxylic acid derivatives are used in the process according to the invention as unsaturated compounds which are hydroformylated in the process according to the invention
- these unsaturated carboxylic acid derivatives are preferably selected from fatty acid esters, preferably from those fatty acid esters which are based on renewable raw materials.
- renewable raw materials are understood to mean, in contrast to petrochemical raw materials which are based on fossil resources such as crude oil or hard coal, such raw materials which are produced or produced on the basis of biomass.
- biomass includes all materials of biological origin, which originate from the so-called “carbon short cycle” and are therefore not part of geological formations or fossil layers under “based on renewable raw materials” and “based on renewable raw materials” that the corresponding proportion of 14 C isotopes in the hydroformylation mixture of the fatty acid esters can be detected by the method ASTM D6866-08 ( 14 C method).
- the identification and quantification of renewable raw materials can be carried out according to ASTM Method D6866. Characteristic for renewable raw materials is their share of the carbon isotope 14 C, in contrast to petrochemical raw materials. With the help of the radiocarbon method, the proportion of 14 C isotopes and thus the proportion of molecules can be determined, which is based on renewable resources.
- the olefins are preferably selected from n-octenes, 1-octene and Cs-containing olefin mixtures.
- phosphoramidites of the formula (I) are preferably used in a first process step: 201300234
- Q is selected from substituted or unsubstituted ⁇ , ⁇ -biphenyl radicals
- R 1 is hydrogen and R 2 is C 1 -C 10 -, preferably C 1 -C 5 -alkyl, substituted or unsubstituted C 4 -C 6 -cycloalkyl or phenyl radicals, and wherein R 2 is not a tert-butyl radical;
- preferred substituted ⁇ , ⁇ -biphenyl radicals are those which in the 3,3 ' and / or 5,5 ' - position of the 1, 1 ' biphenyl-2,2 ' -diolgrund stressess an alkyl radical, preferably a C 1 -C 4 -alkyl radical and particularly preferably have a tert-butyl radical (t-Bu);
- R 2 preferred radicals for R 2 are unbranched and / or branched C 1 -C 5 -alkyl, substituted or unsubstituted C 4 -C 6 -cycloalkyl, phenyl radicals with the exception of one tert-butyl radical (t-Bu);
- Q is selected from substituted or unsubstituted ⁇ , ⁇ -biphenyl radicals
- R 1 is hydrogen and R 2 is C 1 -C 10 -, preferably C 1 -C 5 -alkyl, substituted or unsubstituted C 4 -C 6 -cycloalkyl or phenyl radicals, and wherein R 2 is not a tert-butyl radical
- the transition metal Me is selected from ruthenium, cobalt, rhodium, iridium, and preferably rhodium;
- preferred substituted ⁇ , ⁇ -biphenyl radicals are those which in the 3,3 ' and / or 5,5 ' - position of the 1, 1 ' biphenyl-2,2 ' -diolgrund stressess an alkyl radical, preferably a C 1 -C 4 -alkyl radical and particularly preferably a tert. Butyl (t-Bu) have.
- Preferred radicals for R 2 are unbranched and / or branched C 1 -C 5 -alkyl, substituted or unsubstituted C 4 -C 6 -cycloalkyl, phenyl radicals with the exception of one tert-butyl radical (t-Bu).
- Q is selected from substituted or unsubstituted ⁇ , ⁇ -biphenyl radicals, R 1 is hydrogen and R 2 is C 1 -C 10 -alkyl, preferably C 1 -C 5 -alkyl, substituted or unsubstituted C 4 -C 6 -cycloalkyl or phenyl radicals and wherein R 2 is not a tert-butyl radical;
- ligands of the formula (I) are selected from:
- the unsaturated compounds are added to form a multi-phase reaction mixture; After the end of the reaction, the reaction mixture is separated into aldehydes, alcohols, high boilers, ligands and / or, preferably and degradation products of the catalytically active composition.
- the addition of the unsaturated compounds is preferably carried out together with the precursor of the transition metal and of the ligands (compounds of the formula (I), which is particularly preferred if the 201300234
- the hydroformylation is carried out under conventional reaction conditions, with a temperature of 60 ° C to 160 ° C and a synthesis gas pressure of 1, 0 MPa to 10 MPa are preferred; Particularly preferred are a temperature of 80 ° C to 100 ° C and a synthesis gas pressure of 2.0 MPa to 5.0 MPa.
- 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:
- Q is selected from substituted or unsubstituted ⁇ , ⁇ -biphenyl radicals
- R 1 is hydrogen and R 2 is C 1 -C 10 -, preferably C 1 -C 5 -alkyl, substituted or unsubstituted C 4 -C 6 -cycloalkyl or phenyl radicals, and where R 2 is not tert.- 201300234
- transition metal Me is selected from ruthenium, cobalt, rhodium, iridium and preferably rhodium;
- preferred substituted ⁇ , ⁇ -biphenyl radicals are those which in the 3,3 ' and / or 5,5 ' - position of the 1, 1 ' biphenyl-2,2 ' -diolgrund stressess an alkyl radical, preferably a C 1 -C 4 -alkyl radical and particularly preferably a tert. Butyl (t-Bu);
- R 2 preferred radicals for R 2 are unbranched and / or branched C 1 -C 5 -alkyl, substituted or unsubstituted C 4 -C 6 -cycloalkyl, phenyl radicals with the exception of one tert-butyl radical (t-Bu);
- Q is selected from substituted or unsubstituted ⁇ , ⁇ -biphenyl radicals, R 1 is hydrogen and R 2 is C 1 -C 10 -alkyl, preferably C 1 -C 5 -alkyl, substituted or unsubstituted C 4 -C 6 -cycloalkyl or phenyl radicals and wherein R 2 is not a tert-butyl radical; 201300234
- ⁇ , ⁇ -biphenyl radicals are those which in the 3,3 ' and / or 5,5 ' - position of the 1, 1 ' biphenyl-2,2 ' -diolgrund stressess an alkyl radical, preferably a d- C 4 - Alkyl radical and particularly preferably a tert-butyl radical (t-Bu) have;
- R 2 preferred radicals for R 2 are unbranched and / or branched C 1 -C 5 -alkyl, substituted or unsubstituted C 4 -C 6 -cycloalkyl, phenyl radicals with the exception of one tert-butyl radical (t-Bu);
- ligands of the formula (I) are selected from:
- the process according to the invention is particularly preferably carried out such that 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
- the hydroformylation was preferably 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
- Carbon monoxide-containing gas mixture in the reaction zone bring. This is especially true for unsaturated compounds which are in a liquid state at room temperature and normal pressure. In these cases, the addition of an external solvent is unnecessary, using as solvent the internally formed secondary products such as e.g. those arising from the aldol condensation of the primary product aldehydes, during the reaction in situ.
- reaction was conducted at constant pressure. After the reaction time, the autoclave was cooled to room temperature, expanded with stirring and purged with argon. In each case 1 ml of the reaction mixtures were taken immediately after the stirrer was switched off, diluted with 5 ml of pentane and analyzed by gas chromatography.
- Embodiments of the invention are summarized in Table 1, where also an entry to the use of known under the CAS numbers Registrar [93347-72-9], [31570-04-4] phosphite - tradenames i5 voltage Alkanox 240 ® - refers.
- 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 I order are obtained from a plot of (-ln (1-gain)) versus i o time.
- the increased activity over the control ligands is particularly relevant for use in large scale processes because higher activity means shorter residence times for the target products in the reaction zone, thus optimizing the overall economics of the large scale process.
- MO oleic acid methyl ester (methyl oleate)
- MFS formylstearic acid methyl ester (methyl formyl stearate)
- MS stearic acid methyl ester (methyl stearate)
- ME methyl elaiate (methl elaidate)
- the ligand (1 a) according to the invention shows a high yield in the conversion to the product formyl stearate MFS as well as in the isomerization to the trans isomer of the substrate oleic acid methyl ester, which is denoted as methyl oleate, with only a slight hydrogenation activity, as indicated above, is registered and the phosphorus - rhodium ratio is limited to a maximum of 25: 1.
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Abstract
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EP3184530A1 (de) | 2015-12-21 | 2017-06-28 | Evonik Degussa GmbH | Bidentate diphosphoramidite mit einer homopiperazingruppe als liganden für die hydroformylierung |
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Non-Patent Citations (2)
Title |
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BENETSKIY E ET AL: "Rhodium-Catalyzed Nonisomerizing Hydroformylation of Methyl Oleate Applying Lactame-Based Phosphoramidite Ligands", ACS CATALYSIS, vol. 4, no. 7, 4 June 2014 (2014-06-04), pages 2130 - 2136, XP055516589, ISSN: 2155-5435, DOI: 10.1021/cs500274n * |
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