WO2004026803A1 - Verfahren zur herstellung von dialdehyden und/oder ethylenisch ungesättigten monoaldehyden durch hydroformylierung ethylenisch ungesättigter verbindungen - Google Patents
Verfahren zur herstellung von dialdehyden und/oder ethylenisch ungesättigten monoaldehyden durch hydroformylierung ethylenisch ungesättigter verbindungen Download PDFInfo
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- WO2004026803A1 WO2004026803A1 PCT/EP2003/010166 EP0310166W WO2004026803A1 WO 2004026803 A1 WO2004026803 A1 WO 2004026803A1 EP 0310166 W EP0310166 W EP 0310166W WO 2004026803 A1 WO2004026803 A1 WO 2004026803A1
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- Prior art keywords
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- hydrogen
- aryl
- alkyl
- cycloalkyl
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 61
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 61
- 239000003054 catalyst Substances 0.000 claims abstract description 58
- 239000003446 ligand Substances 0.000 claims abstract description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000013522 chelant Substances 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 8
- 238000007037 hydroformylation reaction Methods 0.000 claims description 69
- -1 hetaryloxy Chemical group 0.000 claims description 57
- 125000003118 aryl group Chemical group 0.000 claims description 52
- 125000000217 alkyl group Chemical group 0.000 claims description 48
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 125000001072 heteroaryl group Chemical group 0.000 claims description 36
- 150000002431 hydrogen Chemical class 0.000 claims description 36
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 29
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 29
- 125000004429 atom Chemical group 0.000 claims description 26
- 229910052736 halogen Inorganic materials 0.000 claims description 24
- 150000002367 halogens Chemical class 0.000 claims description 24
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 21
- 125000003545 alkoxy group Chemical group 0.000 claims description 17
- 150000007942 carboxylates Chemical class 0.000 claims description 16
- 125000004122 cyclic group Chemical group 0.000 claims description 15
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 14
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- 125000002252 acyl group Chemical group 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 150000001768 cations Chemical class 0.000 claims description 9
- 150000001450 anions Chemical class 0.000 claims description 8
- 229910052787 antimony Inorganic materials 0.000 claims description 8
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- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 8
- 125000004104 aryloxy group Chemical group 0.000 claims description 8
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 229910052785 arsenic Inorganic materials 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 239000010948 rhodium Substances 0.000 description 23
- 230000015572 biosynthetic process Effects 0.000 description 19
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 17
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- 238000004821 distillation Methods 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
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- 239000000460 chlorine Chemical group 0.000 description 11
- 229910052801 chlorine Inorganic materials 0.000 description 11
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 10
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- 238000000926 separation method Methods 0.000 description 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 150000001993 dienes Chemical class 0.000 description 7
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 7
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
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- 238000006467 substitution reaction Methods 0.000 description 6
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- 0 C*1c(cccc2)c2-c2c1cccc2 Chemical compound C*1c(cccc2)c2-c2c1cccc2 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 5
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- 125000004437 phosphorous atom Chemical group 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
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- 239000012071 phase Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 description 4
- CXNIUSPIQKWYAI-UHFFFAOYSA-N xantphos Chemical compound C=12OC3=C(P(C=4C=CC=CC=4)C=4C=CC=CC=4)C=CC=C3C(C)(C)C2=CC=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 CXNIUSPIQKWYAI-UHFFFAOYSA-N 0.000 description 4
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- 239000004215 Carbon black (E152) Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- 125000001041 indolyl group Chemical group 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 3
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 2
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- NGDCLPXRKSWRPY-UHFFFAOYSA-N Triptycene Chemical compound C12=CC=CC=C2C2C3=CC=CC=C3C1C1=CC=CC=C12 NGDCLPXRKSWRPY-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 238000010719 annulation reaction Methods 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
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- 125000000524 functional group Chemical group 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
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- 239000002608 ionic liquid Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- VJHGSLHHMIELQD-UHFFFAOYSA-N nona-1,8-diene Chemical compound C=CCCCCCC=C VJHGSLHHMIELQD-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
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- 150000003283 rhodium Chemical class 0.000 description 2
- YNWSXIWHOSSPCO-UHFFFAOYSA-N rhodium(2+) Chemical compound [Rh+2] YNWSXIWHOSSPCO-UHFFFAOYSA-N 0.000 description 2
- PZSJYEAHAINDJI-UHFFFAOYSA-N rhodium(3+) Chemical class [Rh+3] PZSJYEAHAINDJI-UHFFFAOYSA-N 0.000 description 2
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 description 2
- 150000003303 ruthenium Chemical class 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- VOSLXTGMYNYCPW-UHFFFAOYSA-N 1,10-Undecadiene Chemical compound C=CCCCCCCCC=C VOSLXTGMYNYCPW-UHFFFAOYSA-N 0.000 description 1
- 125000005919 1,2,2-trimethylpropyl group Chemical group 0.000 description 1
- 125000001399 1,2,3-triazolyl group Chemical group N1N=NC(=C1)* 0.000 description 1
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- MTNKRTXSIXNCAP-UHFFFAOYSA-N 1-(4-butoxyphenyl)-n-[4-[2-[4-[(4-butoxyphenyl)methylideneamino]phenyl]ethyl]phenyl]methanimine Chemical compound C1=CC(OCCCC)=CC=C1C=NC(C=C1)=CC=C1CCC1=CC=C(N=CC=2C=CC(OCCCC)=CC=2)C=C1 MTNKRTXSIXNCAP-UHFFFAOYSA-N 0.000 description 1
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical class CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- REACWASHYHDPSQ-UHFFFAOYSA-N 1-butylpyridin-1-ium Chemical class CCCC[N+]1=CC=CC=C1 REACWASHYHDPSQ-UHFFFAOYSA-N 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- OFHHDSQXFXLTKC-UHFFFAOYSA-N 10-undecenal Chemical compound C=CCCCCCCCCC=O OFHHDSQXFXLTKC-UHFFFAOYSA-N 0.000 description 1
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 1
- SREXEVLCLYLKQB-UHFFFAOYSA-N 2,7-ditert-butyl-9,9-dimethylxanthene-4,5-diol Chemical compound C1=C(C(C)(C)C)C=C2C(C)(C)C3=CC(C(C)(C)C)=CC(O)=C3OC2=C1O SREXEVLCLYLKQB-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
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- CGWWRMKUJFUTPT-UHFFFAOYSA-N 3-methyl-1h-indole Chemical compound C1=CC=C2C(C)=CNC2=C1.C1=CC=C2C(C)=CNC2=C1 CGWWRMKUJFUTPT-UHFFFAOYSA-N 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 description 1
- 125000003627 8 membered carbocyclic group Chemical group 0.000 description 1
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- USLJTUQADKRCBF-UHFFFAOYSA-N CCOC(Cc(c(C)c1)c[n]1POc1cc(C(C)(C)C)cc2c1OC1C(OC)=CC(C(C)(C)C)=CC1C2(C)C)=O Chemical compound CCOC(Cc(c(C)c1)c[n]1POc1cc(C(C)(C)C)cc2c1OC1C(OC)=CC(C(C)(C)C)=CC1C2(C)C)=O USLJTUQADKRCBF-UHFFFAOYSA-N 0.000 description 1
- GMBFFRKVRGPCQT-UHFFFAOYSA-N CCc1ccc(C(C)c2ccc(CC)[n]2P)[nH]1 Chemical compound CCc1ccc(C(C)c2ccc(CC)[n]2P)[nH]1 GMBFFRKVRGPCQT-UHFFFAOYSA-N 0.000 description 1
- RAIZQIUZLCMHAK-UHFFFAOYSA-N C[n]1c(cccc2)c2c(C(OC)=O)c1 Chemical compound C[n]1c(cccc2)c2c(C(OC)=O)c1 RAIZQIUZLCMHAK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HDTOJNWTFZFLPZ-UHFFFAOYSA-J [K+].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O Chemical compound [K+].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDTOJNWTFZFLPZ-UHFFFAOYSA-J 0.000 description 1
- ROZSPJBPUVWBHW-UHFFFAOYSA-N [Ru]=O Chemical class [Ru]=O ROZSPJBPUVWBHW-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 238000005575 aldol reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 125000005277 alkyl imino group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000012431 aqueous reaction media Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003435 aroyl group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 125000001589 carboacyl group Chemical group 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- ZVENKBGRIGHMRG-UHFFFAOYSA-M carbon monoxide chloro(hydrido)ruthenium triphenylphosphane Chemical compound [C-]#[O+].[H][Ru]Cl.c1ccc(cc1)P(c1ccccc1)c1ccccc1.c1ccc(cc1)P(c1ccccc1)c1ccccc1.c1ccc(cc1)P(c1ccccc1)c1ccccc1 ZVENKBGRIGHMRG-UHFFFAOYSA-M 0.000 description 1
- FMJNZRCLIZWWJP-UHFFFAOYSA-N carbon monoxide;ruthenium;triphenylphosphane Chemical compound [Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FMJNZRCLIZWWJP-UHFFFAOYSA-N 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 1
- 229910000335 cobalt(II) sulfate Inorganic materials 0.000 description 1
- BNGNANCNFVQZBM-UHFFFAOYSA-N cobalt;ethyl hexanoate Chemical compound [Co].CCCCCC(=O)OCC BNGNANCNFVQZBM-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- ZNWNWEHQFXOPGK-UHFFFAOYSA-N decanedial Chemical compound O=CCCCCCCCCC=O ZNWNWEHQFXOPGK-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004420 diamide group Chemical group 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- ZLRAAUUPULJGTL-UHFFFAOYSA-N diaminophosphinous acid Chemical compound NP(N)O ZLRAAUUPULJGTL-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- MQIKJSYMMJWAMP-UHFFFAOYSA-N dicobalt octacarbonyl Chemical group [Co+2].[Co+2].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] MQIKJSYMMJWAMP-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- 238000007700 distillative separation Methods 0.000 description 1
- IYPLTVKTLDQUGG-UHFFFAOYSA-N dodeca-1,11-diene Chemical compound C=CCCCCCCCCC=C IYPLTVKTLDQUGG-UHFFFAOYSA-N 0.000 description 1
- SZCGBFUWBCDIEA-UHFFFAOYSA-N dodecanedial Chemical compound O=CCCCCCCCCCCC=O SZCGBFUWBCDIEA-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- LGYMYODKHKZIEU-UHFFFAOYSA-N heptadeca-1,16-diene Chemical compound C=CCCCCCCCCCCCCCC=C LGYMYODKHKZIEU-UHFFFAOYSA-N 0.000 description 1
- 125000000268 heptanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JEJVUMPKJVMOEZ-UHFFFAOYSA-N hexadeca-1,15-diene Chemical compound C=CCCCCCCCCCCCCC=C JEJVUMPKJVMOEZ-UHFFFAOYSA-N 0.000 description 1
- 125000003104 hexanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- AWJFCAXSGQLCKK-UHFFFAOYSA-N icosa-1,19-diene Chemical compound C=CCCCCCCCCCCCCCCCCC=C AWJFCAXSGQLCKK-UHFFFAOYSA-N 0.000 description 1
- 125000002632 imidazolidinyl group Chemical group 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 125000004628 isothiazolidinyl group Chemical group S1N(CCC1)* 0.000 description 1
- 125000003965 isoxazolidinyl group Chemical group 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001038 naphthoyl group Chemical group C1(=CC=CC2=CC=CC=C12)C(=O)* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- ZICBMHDDLLEGHU-UHFFFAOYSA-N nonadeca-1,18-diene Chemical compound C=CCCCCCCCCCCCCCCCC=C ZICBMHDDLLEGHU-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004010 onium ions Chemical class 0.000 description 1
- 125000000160 oxazolidinyl group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003072 pyrazolidinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006578 reductive coupling reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- YWFDDXXMOPZFFM-UHFFFAOYSA-H rhodium(3+);trisulfate Chemical compound [Rh+3].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YWFDDXXMOPZFFM-UHFFFAOYSA-H 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 description 1
- RADGOBKLTHEUQO-UHFFFAOYSA-N ruthenium(4+) Chemical compound [Ru+4] RADGOBKLTHEUQO-UHFFFAOYSA-N 0.000 description 1
- LHPHHNRKGMRCMY-UHFFFAOYSA-N ruthenium(6+) Chemical compound [Ru+6] LHPHHNRKGMRCMY-UHFFFAOYSA-N 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 125000005346 substituted cycloalkyl group Chemical group 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 125000002130 sulfonic acid ester group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical class CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 1
- XMRSTLBCBDIKFI-UHFFFAOYSA-N tetradeca-1,13-diene Chemical compound C=CCCCCCCCCCCC=C XMRSTLBCBDIKFI-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000001984 thiazolidinyl group Chemical group 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000005490 tosylate group Chemical group 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 125000001834 xanthenyl group Chemical group C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 125000005023 xylyl group Chemical group 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
- C07F9/6596—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having atoms other than oxygen, sulfur, selenium, tellurium, nitrogen or phosphorus as ring hetero atoms
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
- C07C47/12—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen containing more than one —CHO group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
- C07C47/21—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
-
- 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
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/572—Five-membered rings
-
- 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
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/572—Five-membered rings
- C07F9/5728—Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems
-
- 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
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/6552—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a six-membered ring
- C07F9/65522—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a six-membered ring condensed with carbocyclic rings or carbocyclic ring systems
-
- 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
- C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
- C07F9/65586—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system at least one of the hetero rings does not contain nitrogen as ring hetero atom
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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
- C07F9/6581—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
- C07F9/65842—Cyclic amide derivatives of acids of phosphorus, in which one nitrogen atom belongs to the ring
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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
- C07F9/6581—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
- C07F9/65848—Cyclic amide derivatives of acids of phosphorus, in which two nitrogen atoms belong to the ring
Definitions
- the present invention relates to a process for the preparation of dialdehydes and / or ethylenically unsaturated monoaldehydes by hydroformylation of at least one compound having at least two ethylenically unsaturated double bonds in the presence of a catalyst which comprises at least one complex of a metal of VIII. Subgroup with at least one pnicogen ligand.
- Ethylenically unsaturated monoaldehydes (“enals”) and dialdehydes are important intermediates on an industrial scale.
- the aldehyde group can thus easily be converted into a large number of other functional groups such as amino, hydroxyl, carboxy group etc.
- Enaien a large number of compounds are obtained that are difficult to access on other synthetic routes and are suitable as bifunctional synthetic building blocks for subsequent reactions.
- Dialdehydes and the diols, diamines and dicarboxylic acids obtainable from them are suitable for a large number of applications, eg. B. for the production of polyesters and polyamides and as a crosslinking agent for polymers.
- catalysts for the hydroformylation of polyethylenically unsaturated compounds are to be distinguished by high activity at the lowest possible temperatures and the lowest possible reaction pressures in order to avoid undesirable side reactions, such as, for example, B. to avoid the aldol reaction.
- Van der Slot et al., Organometallics 19., 2504 (2000) describe the synthesis of phosphorodiamide chelate ligands with a bisphenol or xanthene backbone, the diamide unit of which is formed by biuret groups, and the catalytic properties of the rhodium complexes thereof Hydroformylation compounds.
- WO 00/56451 on phosphorato relates, inter alia, to cyclic oxaphosphorines substituted with pyrrole derivatives and the use of these as ligands in catalysts for hydroformylation.
- WO 01/58589 describes compounds of phosphorus, arsenic and antimony based on diaryl-fused bicyclo [2.2.2] basic bodies and catalysts which contain these as ligands.
- DE-A-100 23 471 describes a process for hydroformylation using a hydroformylation catalyst which comprises at least one phosphine ligand which has two triarylphosphine groups, an aryl radical of the two triarylphosphine groups in each case via a single bond to a nonaromatic 5- is linked to 8-membered carbocyclic or heterocyclic bridging group.
- the phosphorus atoms also have hetaryl groups as further substituents.
- DE-A-100 46 026 describes a hydroformylation process in which the catalyst used is a complex based on a phosphorus, arsenic or antimony-containing compound as ligand, this compound in each case two a P-, As- or Sb- Ato and at least two further heteroatom-containing groups bound to a xanthene-like molecular structure.
- US Pat. No. 5,710,344 relates to the hydroformylation of olefins by means of rhodium catalysts which can be modified with chelate phosphorodiamidite ligands with a bisphenol or bisnaphthol backbone and whose phosphorus atoms can carry unsubstituted pyrrolyl, imidazolyl or indolyl groups.
- rhodium catalysts which can be modified with chelate phosphorodiamidite ligands with a bisphenol or bisnaphthol backbone and whose phosphorus atoms can carry unsubstituted pyrrolyl, imidazolyl or indolyl groups.
- olefin a. 1,3-butadiene used.
- Rh (acac) (CO) P (C 6 H 5 ) 3 ) / P (C 6 H 5 ) 3 .
- Rh (acac) (CO) P (C 6 H 5 ) 3 ) / P (C 6 H 5 ) 3 .
- the formation of a large number of isomeric mono- and dialdehydes is observed.
- the n-selectivity of these catalyst systems is inadequate for the targeted production of ⁇ , ⁇ -enals or dialdehydes.
- WO 03/018192 describes a hydroformylation process using a catalyst complex which has as ligands at least one pyrrole-phosphorus compound in which a substituted and / or pyrrole group which is integrated into a fused ring system is covalently linked to the phosphorus atom via its pyrrolic nitrogen atom.
- the unpublished international application PCT / EP 03/01245 describes phosphorus chelate compounds in which three nitrogen atoms, which are themselves part of an aromatic ring system, are covalently bound to the two phosphorus atoms, and their use as ligands for hydroformylation catalysts.
- WO 02/083695 describes u.
- These ligands have two groups containing pnicogen atoms which are connected to one another via a xanthene-like or triptycene-like molecular structure and where at least one pyrrole group is covalently bound to each pnicogen atom via the nitrogen atom thereof.
- di- or polyenes are also mentioned in general in addition to a large number of others. Embodiments with these olefins are not included.
- the present invention is based on the object of providing a process for the hydroformylation of compounds having at least two ethylenically unsaturated double bonds under the mildest possible pressure and / or temperature conditions with short reaction times and / or catalyst loads.
- the highest possible proportion of ⁇ , ⁇ -dialdehydes and / or ⁇ , ⁇ -enals with good conversion should preferably be achieved (high n-selectivity).
- the isomerization of ethylenically unsaturated double bonds in the molecule should be avoided as far as possible. In particular, the catalyst service lives should also be long.
- the hydroformylation catalyst used being at least one complex of a metal of the VIII.
- Subsidiary group with at least one pnicogen chelate ligand which has two groups containing pnicogen atoms which have a xanthene -like or triptycene-like molecular framework are connected to one another and wherein at least one pyrrole group is covalently bonded to each pnicogen atom via its nitrogen atom.
- the invention therefore relates to a process for the preparation of dialdehydes and / or ethylenically unsaturated monoaldehydes by reacting at least one compound having at least two ethylenically unsaturated double bonds with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst which comprises at least one complex of a metal from subgroup VIII comprising at least one ligand selected from pnicogen chelate compounds of the general formula I,
- a 1 and A 2 independently represent 0, S, SiR a R b , NR C or CR d R e , where
- R a , R b and R c independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
- R d and R e independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl or the group R d together with another group R d or the group R e together with another group R e is an intramolecular bridge group D form,
- R 9 and R 1 independently of one another represent hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, carboxyl, carboxylate or cyano or are bonded to one another to form a C 3 -C -alkylene bridge,
- c is 0 or 1 (if c is 0, there is no direct bond between ⁇ 1 and A 2 )
- R 1 , R 11 , R 111 , R IV , R v and R VI independently of one another for hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, C00R f , C00-M +, S0 3 R f , SO ⁇ 3 M + , NE X E 2 , NE l E 2 E 3+ ", Alky- Ien-NE 1 E 2 E 3+ X-, OR f , SR f , (CHR3CH 2 0) x R f , (CH 2 N (E l )) x R f , (CH 2 CH 2 N (E l )) x R f , halogen, trifluoromethyl, nitro, acyl or cyano,
- R f , E 1 , E 2 and E 3 each represent the same or different radicals selected from hydrogen, alkyl, cycloalkyl or aryl,
- R9 represents hydrogen, methyl or ethyl
- x represents an integer from 1 to 120
- two adjacent radicals selected from R 1 , R 11 , R 111 , Ri v , R and R VI together with two adjacent carbon atoms of the benzene nucleus to which they are attached, represent a condensed ring system with 1, 2 or 3 further rings .
- Pn represents a pnicogen atom selected from the elements phosphorus, arsenic or antimony
- R 1, R 2 , R 3 , R 4 independently of one another represent hetaryl, hetaryloxy, alkyl, alkoxy, aryl, aryloxy, cycloalkyl, cycloalkoxy, heterocycloalkyl, heterocycloalkoxy or an NE i E group, with the proviso that R x and R 3 are pyrrole groups bonded to the pnicogen atom Pn via the nitrogen atom
- Py is a pyrrole group which is bonded to the pnicogen atom Pn via the pyrrolic nitrogen atom,
- I stands for a chemical bond or for 0, S, SiR a R b , NR C , optionally substituted C ⁇ -C ⁇ o alkylene or CRkR 1 ,
- W represents cycloalkyl, cycloalkoxy, aryl, aryloxy, hetaryl or hetaryloxy,
- R h and R 1 independently of one another for hydrogen, alkyl
- R 1 together with R 2 and / or R 3 together with R 4 is a bispyrrole group of the formula which is bonded to the pnicogen atom Pn via the nitrogen atoms
- the present invention relates to a process for the hydroformylation of compounds which contain at least two ethylenically unsaturated double bonds, with isolation of the unsaturated monoaldehydes formed.
- the term “proportion of linear dialdehyde” (both double bonds are hydroformylated at the end) means the proportion of n, n-dialdehyde formed based on the sum of the n, n-, n, iso- and iso, iso-dialdehydes.
- the n component is therefore calculated using the following equation:
- alkyl' includes straight chain and branched alkyl groups. It is preferably straight-chain or branched C 1 -C 2 -alkyl, preferably C ⁇ -C ⁇ 2 -alkyl, particularly preferably C ⁇ -C 8 -alkyl and very particularly preferably C ⁇ -C-alkyl groups.
- alkyl groups are in particular methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl,
- alkyl also includes substituted alkyl groups which generally have 1, 2, 3, 4 or 5, preferably 1, 2 or 3 and particularly preferably 1, substituents selected from the groups cycloalkyl, aryl, hetaryl, halogen, NE 1 E 2 , NE l E 2 E 3+ , carboxyl, carboxylate, -S0 3 H and sulfonate.
- alkylene for the purposes of the present invention stands for straight-chain or branched alkanediyl groups with 1 to 4 carbon atoms.
- cycloalkyl encompasses unsubstituted and substituted cycloalkyl groups, preferably C 5 to C 7 cycloalkyl groups, such as cyclopentyl, Cyclohexyl or cycloheptyl, which in the case of a substitution, in general 1, 2, 3, 4 or 5, preferably 1, 2 or 3 and particularly preferably 1, selected from the groups alkyl, alkoxy and halogen, can carry.
- heterocycloalkyl in the context of the present invention encompasses saturated, cycloaliphatic groups with generally 4 to 7, preferably 5 or 6 ring atoms, in which 1 or 2 of the ring carbon atoms are replaced by heteroatoms selected from the elements oxygen, nitrogen and sulfur and which may optionally be substituted, where in the case of a substitution, these heterocycloaliphatic groups 1, 2 or 3, preferably 1 or 2, particularly preferably 1, selected from alkyl, aryl, C00R f , COO ⁇ M + and NE ⁇ -E 2.
- heterocycloaliphatic groups are pyrrolidinyl, piperidinyl, 2,2, 6, 6-tetramethyl-piperidinyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, morpholidinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinylothiophenyl and tetrahedronyl , Tetrahydrofuranyl, Tetrahydropyrany1, Dioxanyl called.
- aryl encompasses unsubstituted and substituted aryl groups, and preferably stands for phenyl, tolyl, xylyl, mesityl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl or naphthacenyl, particularly preferably for phenyl or naphthyl, where these Aryl groups in the case of a substitution in general 1, 2, 3, 4 or 5, preferably 1, 2 or 3 and particularly preferably 1 substituent, selected from the groups alkyl, alkoxy, carboxyl, carboxylate, trifluoromethyl, -S0 3 H, sulfonate, NE X E 2 , alkylene-NE 1 E 2 , nitro, cyano or halogen.
- heterocycloaromatic groups preferably the groups pyridyl, quinolinyl, acridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, and the subgroup of the “pyrrole group”, these heterocycloaromatic groups being substituted in the general 1, 2 or 3 substituents selected from the groups alkyl, alkoxy, carboxyl, carboxylate, -S0 3 H, sulfonate, NE X E 2 , alkylene-NE I E 2 , trifluoromethyl or halogen.
- pyrrole group stands for a series of unsubstituted or substituted, heterocycloaromatic groups which are structurally derived from the pyrrole backbone and contain a pyrrolic nitrogen atom in the heterocycle which is covalent with other atoms, for example, a pnicogen atom.
- pyrrole group thus includes the unsubstituted or substituted groups pyrrolyl, imidazolyl, pyrazolyl, indolyl, purinyl, indazolyl, benzotriazolyl, 1,2, 3-triazolyl, 1,3,4-triazolyl and carbazolyl, which in the case of a Substitution in general 1, 2 or 3, preferably 1 or 2, particularly preferably 1, selected from the groups alkyl, alkoxy, acyl, carboxyl, carboxylate, -S0 3 H, sulfonate, NE I E 2 , alkylene-NE I E 2 , trifluoromethyl or halogen.
- bispyrrole group in the context of the present invention includes double-bonded groups of the formula
- the bispyrrole groups can also be unsubstituted or substituted and, in the case of substitution per pyrrole group unit, generally 1, 2 or 3, preferably 1 or 2, in particular 1, substituents selected from alkyl, alkoxy, carboxyl, carboxylate, -S0 3 H, sulfonate, NE X E 2 , alkylene-NE I E 2 , trifluoromethyl or halogen, with these details of the number of possible substituents linking the pyrrole group units by direct chemical bonding or by means of the linkage mediated by the above-mentioned groups is not considered a substitution.
- Carboxylate and sulfonate in the context of this invention preferably represent a derivative of a carboxylic acid function or a sulfonic acid function, in particular a metal carboxylate or sulfonate, a carboxylic acid or sulfonic acid ester function or a carboxylic acid or sulfonic acid amide function.
- these include e.g. B. the esters with C ⁇ -C alkanols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and tert-butanol.
- acyl stands for alkanoyl or aroyl groups with generally 2 to 11, preferably 2 to 8, carbon atoms, for example for the acetyl, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl, 2-ethyl-hexanoyl, 2-propylheptanoyl, benzoyl or naphthoyl group.
- the groups NE X E 2 and NE 4 E 5 preferably represent N, N-dimethylamino, N, N-diethylamino, N, N-dipropylamino, N, N-diisopropylamino, N, N-di-n- butylamino, N, N-di-t-butylamino, N, N-dicyclohexylamino or N, N-diphenylamino.
- Halogen represents fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.
- M + stands for a cation equivalent, ie for a monovalent cation or the portion of a multivalent cation corresponding to a positive single charge.
- the cation M + serves only as a counterion for the neutralization of negatively charged substituent groups, such as the C00- or the sulfonate group, and can in principle be chosen as desired.
- Alkali metal ions in particular Na + , K + , Li + ions or onium ions, such as ammonium, mono, di, tri, tetraalkylammonium, phosphonium, tetraalkylphosphonium or tetraarylphosphonium ions are therefore preferred used.
- anion equivalent X " which serves only as a counterion of positively charged substituent groups, such as the ammonium groups, and can be chosen arbitrarily from monovalent anions and the proportions of a polyvalent anion corresponding to a negative single charge, wherein halide ions X- are generally preferred , especially chloride and bromide.
- the values for x stand for an integer from 1 to 240, preferably for an integer from 3 to 120.
- Condensed ring systems can be aromatic, hydroaromatic and cyclic compounds linked by fusing.
- Condensed ring systems consist of two, three or more than three rings.
- Preferred among the condensed ring systems are ortho-condensed ring systems.
- Y represents a chemical bond, i.e. the point of attachment of the bridging group Q to the groups -O-, or in the case when a and / or b is 0, to the groups PnR 1 R 2 or PnR 3 R 4 .
- the groups A 1 and A 2 can generally stand independently of one another for 0, S, SiR a R b , NR C or CR d R e , the substituents R a , R b and R c generally being independent of one another can be hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, whereas the groups R d and R e independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl or the group R d together with a further group R d or the group R e together with another group R e can form an intramolecular bridge group D.
- D is a double-bonded bridge group that is generally selected from the groups
- R 9 and R 10 independently of one another represent hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, carboxyl, carboxylate or cyano or are connected to one another to form a C 3 -C -alkylene group and R u , R i2 , R i3 and R i4 independently of one another for hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, COOH, carboxylate, cyano, alkoxy, S0 3 H, sulfonate, NE X E 2 , alk len-NE l E ⁇ 3 "1 ⁇ -, aryl or nitro, preferably the groups R 9 and R 10 are hydrogen, C ⁇ -C 10 alkyl or Carboxylate and the groups R 11 , R i2 , R X3 and R i4 for hydrogen, C ⁇ -C ⁇ o-alkyl, halogen, in particular fluorine
- R 9 , R 10 , R u , R i2 , R X3 and R i4 are particularly preferably hydrogen.
- such pnicogen chelate compounds are preferred in which 1, 2 or 3, preferably 1 or 2, in particular 1 of the groups R u , R i2 , R i3 and / or R i4 for a C00-Me + , a S0 3 "M + or a NE I E 2 E 3+ ⁇ -- group, where M + and X- have the meaning given above.
- Particularly preferred bridge groups D are the ethylene group
- R d forms an intramolecular bridging group D with another group R d or R e with another group R e , then the index c in this case is 1.
- those bridge groups Q are preferred in which A 1 is different from A 2 , where A 1 is preferably a CR d R e group and A 2 is preferably an O or S group, particularly preferably an oxa group 0.
- Particularly preferred bridging groups Q are thus those which consist of a triptycene like or xanthene type (A 1: 0: CR d R e, A 2) are constructed scaffolding.
- R 1 , R 11 , R ⁇ I ⁇ Riv R V and ⁇ RVI s i n d preferably selected from hydrogen, alkyl, alkoxy, cycloalkyl, hetero- cycloalkyl, aryl and hetaryl.
- R 1 , R 11 , R 111 , R IV , R v and R VI are hydrogen f.
- R 1 and R VI are independently C ⁇ -C-alkyl or C ⁇ -C 4 alkoxy.
- R 1 and R VI are preferably selected from methyl, ethyl, isopropyl, tert-butyl and methoxy.
- R 11 , R 111 , R IV and R v are preferably hydrogen.
- R 11 and R v independently of one another are C ⁇ -C 4 -alkyl or C ⁇ -C 4 -alkoxy.
- R 11 and R v are preferably selected from methyl, ethyl, isopropyl, tert-butyl and methoxy.
- R 1 , R 111 , R IV and R VI in these compounds are preferably hydrogen.
- the rings are preferably benzene or naphthalene rings.
- Fused benzene rings are preferably unsubstituted or have 1, 2 or 3, in particular 1 or 2, substituents which are selected from alkyl, alkoxy, halogen, SO 3 H, sulfonate, NE X E 2 , alkylene-NElE 2 , trifluoromethyl, nitro, C00R f , alkoxycarbonyl, acyl and cyano.
- Fused naphthalene rings are preferably unsubstituted or have a total of 1, 2 or 3, in particular 1 or 2, of the substituents mentioned above for the fused benzene rings in the non-fused ring and / or in the fused ring.
- At least one of the radicals R 1 is present .
- R 11 , R 111 , R IV , R v and / or R VI for a polar (hydrophilic) group water-soluble pnicogen chelate complexes then generally resulting when complexing with a Group VIII metal.
- the polar groups are preferably selected from C0OR f , COO-M ", S0 3 R f , S0 3 -M" * ", NElE 2 , alkylene-NE l E 2 , NE l E 2 E 3+ X", alkylene NE l E 2 E 3+ ⁇ -, 0R f , SR f , (CHR9CH 2 0) x R f or (CH 2 CH 2 N (E l )) x R f , where R f , E 1 , E 2 , E 3 , RS, M +, X ⁇ and x have the meanings given above.
- the bridge group Q is connected via the chemical bond Y either directly or via an oxa group O to the groups PnR i R 2 or PnR 3 R 4 .
- Pn stands for an atom from the pnicogen group, selected from phosphorus, arsenic or antimony. Pn particularly preferably represents phosphorus.
- the individual picnicogen atoms Pn of the picnicogen chelate compounds used according to the invention are each covalent via two Bonds connected to two substituents R 1 and R 2 or R 3 and R 4 , the substituents R 1 , R 2 , R 3 and R 4 independently of one another for hetaryl, hetaryloxy, alkyl, alkoxy, aryl, aryloxy, cycloalkyl, cycloalkoxy , Heterocycloalkyl, heterocycloalkoxy or a NE i E 2 group, with the proviso that R i and R 3 are pyrrole groups bonded to the pnicogen atom Pn via the pyrrolic nitrogen atom.
- the substituents R 2 and / or R 4 are also advantageously pyrrole groups bonded to the pnicogen atom Pn via the pyrrolic nitrogen atom. Furthermore, the substituent R 1 together with the substituent R 2 and / or the substituent R 3 together with the substituent R 4 can advantageously form a bispyrrole group bonded to the pnicogen atom Pn via the pyrrolic nitrogen atoms.
- a hydroformylation catalyst is used in the process according to the invention, in which the radicals R 1 , R 2 , R 3 and R 4 are selected independently of one another from groups of the formulas Ia to Ik:
- Alk is a C ⁇ -C 4 alkyl group
- Hydroformylation catalysts based on ligands which have one or more 3-methylindolyl group (s) bonded to the phosphorus atom are distinguished by a particularly high stability and thus particularly long catalyst life.
- the substituent R 1 together with the substituent R 2 or the substituent R 3 together with the substituent R 4 can contain a divalent group of the formula containing pyrrole group bonded to the pnicogen atom Pn via the pyrrolic nitrogen atom
- Py is a pyrrole group
- I stands for a chemical bond or for O, S, SiR a R b , NR C or CR h R i ,
- W represents cycloalkyl, cycloalkoxy, aryl, aryloxy, hetaryl or hetaryloxy
- R h and R 1 independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
- Hydroformylation catalysts which comprise at least one ligand of the formula I are preferably used in the process according to the invention, in which the substituent R 1 together with the substituent R 2 or the substituent R 3 together with the substituent R 4 is a bispyrene group of the formula
- I stands for a chemical bond or for 0, S, SiR a R b , NR C or optionally substituted C ⁇ -C ⁇ 0 alkylene, preferably CR k R 1 , in which R a , R b , R c , R h and R 1 independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
- R 3 l, R 3! ', R 32 , R 32 ', R 33 , R 33 ', R 34 and R 34 ' independently of one another for hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, W'C00R a , WC00-M + , W '( S0 3 ) R f , W '(S0 3 ) "M + , W'P0 3 (R f ) (R g ) W' (P0 3 ) 2 - (M + ) 2 , W'NE l E 2 , W '(NE l E 2 E 3 ) + X ⁇ , W'0R f , W'SR f , (CHR ⁇ 3CH 2 0) x R f , (CH 2 NE l ) x Rf, (CH 2 CH 2 NEl) x R f are halogen, trifluoromethyl,
- W ' represents a single bond, a heteroatom or a divalent bridging group with 1 to 20 bridge atoms
- R f , E 1 , E 2 , E 3 each represent the same or different radicals selected from hydrogen, alkyl, cycloalkyl or aryl,
- R9 represents hydrogen, methyl or ethyl, 0
- M + stands for a cation equivalent.
- 5 x represents an integer from 1 to 240
- I is preferably a chemical bond or a C ⁇ -C 4 alkylene group, particularly preferably a methylene group.
- the pnicogen chelate compounds used according to the invention are selected from compounds of the general formula II
- R i5 , R i6 , R i? and R X8 independently of one another for hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, W'COOR k , WC0O-M +, W '(S0 3 ) R k , W' (S0 3 ) -M +, W'P0 3 ( R k ) (R 1 ) W '(P0 3 ) 2 ⁇ (M + ) 2 ,
- W ' represents a single bond, a hetero atom or a divalent bridging group with 1 to 20 bridge atoms
- R k f E 4 , E 5 , E 6 each represent the same or different radicals selected from hydrogen, alkyl, cycloalkyl or aryl,
- R 1 represents hydrogen, methyl or ethyl
- y represents an integer from 1 to 240
- R X9 and R 20 independently of one another represent cycloalkyl, heterocycloalkyl, aryl or hetaryl,
- a and b independently of one another denote the number 0 or 1
- Pn represents a pnicogen atom selected from the elements phosphorus, arsenic or antimony, preferably phosphorus,
- Q is a bridge group as previously defined.
- the picnicogen atoms Pn are preferably both phosphorus.
- bridge group Q With regard to suitable and preferred embodiments of bridge group Q, reference is made in full to the previous statements.
- the radicals R i5 to R 18 can each independently have the same or different meanings.
- Compounds of the formula II are preferred in which the pyrrole groups in the 2-position, 2,5-position or 3,4-position carry a substituent other than hydrogen.
- the substituents R i5 to R X8 which are different from hydrogen are preferably selected independently of one another from C ⁇ ⁇ to Cg-, preferably C ⁇ ⁇ to C 4 alkyl, especially methyl, ethyl, isopropyl and tert-butyl, alkoxycarbonyl, such as methoxycarbonyl, ethoxycar- bonyl, isopropyloxycarbonyl and tert-butyloxycarbonyl and trifluoromethyl.
- Preferred compounds of the general formula II are those in which the radicals R 5 and R i6 and / or R 17 and R i8 together with the carbon atoms of the pyrrole ring to which they are attached represent a condensed ring system with 1, 2 or 3 further rings , If R 15 and R i6 and / or R i7 and R i8 stand for a fused-on, ie fused-on ring system, then it is preferably benzene or naphthalene rings.
- Fused benzene rings are preferably unsubstituted and have 1, 2 or 3, in particular 1 or 2, substituents which are selected from alkyl, alkoxy, halogen, SO 3 H, sulfonate, NE 4 E 5 , alkylene-NE 4 E 5 , Trifluoromethyl, nitro, C00R k , alkoxycarbonyl, acyl and cyano.
- Fused naphthalene rings are preferably unsubstituted or have in non-fused ring and / or in the fused ring each 1, 2 or 3, in particular 1 or 2 of the substituents previously mentioned for the fused benzene rings.
- R 17 and R i8 are preferably 5 or R 18 is hydrogen and R 17 is a substituent which is selected from C ⁇ ⁇ to Cs-alkyl, preferably C ⁇ ⁇ to C 4 alkyl, especially methyl, ethyl, isopropyl or tert. -Butyl.
- At least one of the radicals R i5 , R i ⁇ , R 17 and / or R 1 represents a polar (hydrophilic) group, in which case, as a rule, in the formation of the complex a Group VIII metal water-soluble complexes result.
- the compounds of the formula II are preferably selected from compounds of the general formulas II.1 to II.3
- R i5 , R i6 , R i? , R i8 , Q, a and b have the meanings given above, where in formula II.3 at least one of the radicals R X6 or R 17 is not hydrogen,
- R X9 and R 20 independently of one another are cycloalkyl, heterocycloalkyl, aryl or hetaryl.
- R i5 to R i8 are preferably all hydrogen.
- R i5 and R i8 preferably represent hydrogen and are R 16 and R i? selected from C ⁇ -Cg-alkyl, preferably C ⁇ -C 4 alkyl, such as methyl, ethyl, isopropyl and tert-butyl.
- the radicals R i6 and R l? selected from C ⁇ -Cs-alkyl, particularly preferably C ⁇ -C 4 alkyl, such as methyl, ethyl, isopropyl and tert-butyl, and C00R k , wherein R k for C ⁇ -C alkyl, such as methyl, ethyl, isopropyl and tert-butyl is.
- catalytically active species of the general formula H g Z d (C0) e G f are formed from the catalysts or catalyst precursors used in each case, in which Z represents a metal of subgroup VIII, G represents a phosphorus or arsenic group. or antimony-containing ligands of the formula I or II and d, e, f, g are natural numbers, depending on the valency and type of the metal and the binding force of the ligand G.
- e and f are independently at least 1, such as. B. 1, 2 or 3.
- the sum of e and f is preferably from 2 to 5.
- the complexes of the metal Z with the ligands G used according to the invention can, if desired, additionally at least one further ligand not used according to the invention, eg. B. from the class of triarylphosphines, especially triphenylphosphine, triarylphosphites, triarylphosphinites, triarylphosphonites, phosphabenzenes, trialkylphosphines or phosphametallocenes.
- Such complexes of the metal Z with ligands used according to the invention and not used according to the invention form, for. B. in an equilibrium reaction after adding a ligand to a complex of the general formula H g Z d (C0) e G f .
- the hydroformylation catalysts are prepared in situ in the reactor used for the hydroformylation reaction. If desired, however, the catalysts of the process according to the invention can also be prepared separately and isolated by customary processes. To prepare the catalysts in situ, at least one compound of the general formula I or II, a compound or a complex of a metal from subgroup VIII, if desired one or more additional ligands and optionally an activating agent in an inert solvent under the hydroformylation conditions implement.
- Suitable rhodium compounds or complexes are e.g. B. rhodium (II) and rhodium (III) salts, such as rhodium (III) chloride, rhodium (III) nitrate, rhodium (III) sulfate, potassium rhodium sulfate, Rhodiu (II) - or rhodium ( III) carboxylate, rhodium (II) and rhodium (III) acetate, rhodium (III) oxide, salts of rhodium (III) acid, trisammonium hexachlororhodate (III) etc.
- B. rhodium (II) and rhodium (III) salts such as rhodium (III) chloride, rhodium (III) nitrate, rhodium (III) sulfate, potassium rhodium sul
- rhodium complexes such as rhodium biscarbonylacetylacetonate, ace- tylacetonatobisethylene rhodium (I) etc.
- Rhodium biscarbonylacetylacetonate or rhodium acetate are preferably used.
- Ruthenium salts or compounds are also suitable. Suitable ruthenium salts are, for example, ruthenium (III) chloride, ruthenium (IV) -, ruthenium (VI) - or ruthenium (VIII) oxide, alkali metal salts of ruthenium oxygen acids such as KRuO 4 or KRu0 4 or complex compounds, such as, for. B. RuHCl (CO) (PPh 3 ) 3 .
- the metal carbonyls of ruthenium such as trisruthenium dodecacarbonyl or hexaruthenium octadecacarbonyl, or mixed forms in which CO is partially replaced by ligands of the formula PR 3 , such as Ru (CO) 3 (PPh 3 ) 2 , can also be used in the process according to the invention.
- Suitable cobalt compounds are, for example, cobalt (II) chloride, cobalt (II) sulfate, cobalt (II) carbonate, cobalt (II) nitrate, their amine or hydrate complexes, cobalt carboxylates such as cobalt acetate, cobalt ethyl hexanoate and cobalt naphthenoate.
- cobalt carboxylates such as cobalt acetate, cobalt ethyl hexanoate and cobalt naphthenoate.
- the carbonyl complexes of cobalt such as dicobalt octacarbonyl, tetrakobalt dodecacarbonyl and hexacobalt hexadecacarbonyl can be used.
- Suitable metals of subgroup VIII are in particular cobalt and rhodium.
- the solvents used are preferably the aldehydes which are formed in the hydroformylation of the respective olefins, and their higher-boiling secondary reaction products, for. B. the products of aldol condensates.
- suitable solvents are aromatics, such as toluene and xylenes, hydrocarbons or mixtures of hydrocarbons, also for diluting the above-mentioned aldehydes and the secondary products of the aldehydes.
- Other solvents are esters of aliphatic carboxylic acids with alkanols len, for example Essigester or Texanol ®, ethers such as tert-butyl methyl ether and tetrahydrofuran.
- ligands are sufficiently hydrophilized, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ketones such as acetone and methyl ethyl ketone etc. can also be used. Furthermore, as a solvent, so-called “ionic liquids" ver ⁇ be spent.
- liquid salts for example N, N'-dialkylimidazolium salts such as the N-butyl-N'-methylimidazolium salts, tetraalkylammonium salts such as the tetra-n-butylammonium salts, N-alkylpyridinium salts such as the n-butylpyridinium salts, tetraalkylphosphonium salts, tetraalkylphosphonium salts Trishexyl (tetra-decyl) phosphonium salts, e.g. B. the tetrafluoroborates, acetates, Tetrachloroaluminates, hexafluorophosphates, chlorides and tosylates.
- N, N'-dialkylimidazolium salts such as the N-butyl-N'-methylimidazolium salts
- tetraalkylammonium salts such as the
- aqueous solvent systems which, in addition to water, contain a water-miscible solvent, for example an alcohol such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, a ketone such as acetone and methyl ethyl ketone or contain another solvent.
- the reactions then take the form of a two-phase catalysis, the catalyst being in the aqueous phase and feedstocks and products forming the organic phase.
- the implementation in the "ionic liquids" can also be designed as a two-phase catalysis.
- all compounds which contain at least two ethylenically unsaturated double bonds are suitable as substrates for the hydroformylation process according to the invention. These include, for example, di- or polyenes with isolated or conjugated double bonds. Suitable diolefins are, for example, compounds of the formula F
- X a , X b , X d X e , X f , X ⁇ 3 each independently represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, and X c represents a single bond or C ⁇ -C 20 alkanediyl , which optionally one or more, for example 1, 2, 3, 4 or 5, substituents selected from the group cycloalkyl, aryl, hetaryl, halogen, C,-C 20 alkoxy, C ⁇ -C 20 alkoxycarbonyl, E i E 2 , carries and / or is optionally interrupted by at least one further double bond and / or is part of one or more cycloalkyl groups, heterocycloalkyl groups, aryl groups or hetaryl groups, it being possible for the cycloalkyl groups and heterocycloalkyl groups to be partially unsaturated.
- the compound used for the hydroformylation with at least two ethylenically unsaturated double bonds is preferably selected from diolefins with one terminal and one internal double bond and ⁇ , ⁇ -diolefins, ie dioefins with two terminal double bonds.
- the ⁇ , ⁇ -diolefins include, for example, 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-hepadiene, 1,7-octadiene, 1,8-nonadiene, 1,9 -Decadiene, 1, 10-undecadiene, 1, 11-dodecadiene, 1.12-tridecadiene, 1, 13-tetradecadiene, 1.14-pentadecadiene, 1, 15-hexadecadiene, 1, 16-heptadecadiene, 1, 17 -0ctadecadiene, 1, 18-nonadecadiene, 1, 19-icosadiene and mixtures thereof.
- a diolefin or diolefin mixture which is commercially available is preferably used in the hydroformylation process according to the invention, preferably a mixture containing ⁇ , ⁇ -diolefins.
- These include e.g. B. 1,3-butadiene-containing hydrocarbon mixtures.
- the 1,3-butadiene is separated from these to obtain the so-called raffinate I.
- Pure 1,3-butadiene can generally e.g. B. be isolated by extractive distillation from commercially available hydrocarbon mixtures.
- 1,5-Hexadiene and 1,9-Decadiene are manufactured on an industrial scale by Shell.
- 1,7-0ctadiene is obtained for example by reductive coupling of 1,3-butadiene in the presence of acetic acid and triethylamine as promoters.
- a process is preferred which is characterized in that the hydroformylation catalyst is prepared in situ, using at least one compound of the formula I or II, a compound or a complex of a metal from subgroup VIII and, if appropriate, an activating agent in an inert solvent brings the hydroformylation conditions to reaction.
- the ligand-metal complexes can also be prepared separately and isolated by customary methods.
- the hydroformylation reaction can be carried out continuously, semi-continuously or batchwise.
- Suitable reactors for the continuous reaction are known to the person skilled in the art and are described, for. B. in Ullmann's Encyclopedia of Industrial Chemistry, Vol. 1, 3rd Edition, 1951, pp. 743 ff. ben.
- Suitable pressure-resistant reactors are also known to the person skilled in the art and are described, for. B. in Ullmann's Encyclopedia of Industrial Chemistry, Vol. 1, 3rd Edition, 1951, pp. 769 ff.
- an autoclave is used for the method according to the invention, which can, if desired, be provided with a stirring device and an inner lining.
- composition of the synthesis gas of carbon monoxide and hydrogen used in the process according to the invention can vary within wide ranges.
- the molar ratio of carbon monoxide and hydrogen is usually about 5:95 to 70:30, preferably about 40:60 to 60:40.
- a molar ratio of carbon monoxide and hydrogen in the range of approximately 1: 1 is particularly preferably used.
- the temperature in the hydroformylation reaction is generally in a range from approximately 20 to 180 ° C., preferably approximately 40 to 80 ° C., in particular approximately 50 to 70 ° C.
- the reaction is usually carried out at the partial pressure of the reaction gas at the selected reaction temperature.
- the pressure is in a range from about 1 to 700 bar, preferably 1 to 600 bar, in particular 1 to 300 bar.
- the reaction pressure can be varied depending on the activity of the hydroformylation catalyst used.
- the catalysts based on phosphorus, arsenic or antimony-containing pnicogen chelate compounds allow reaction in a range of low pressures, such as in the range from 1 to 100 bar, preferably 5 to 50 bar.
- the molar ratio of pnicogen chelate compound I or II to the metal of subgroup VIII in the hydroformylation medium is generally in a range from about 1: 1 to 1000: 1, preferably from 1: 1 to 100: 1, in particular from 1: 1 to 50: 1 and very particularly preferably 1: 1 to 20: 1.
- the molar ratio of metal of VIII is usually Subgroup to substrate below 1 mol%, preferably below 0.5 mol% and in particular below 0.1 mol% and very particularly preferably below 0.05 mol%.
- the hydroformylation catalysts can be separated from the discharge of the hydroformylation reaction by customary processes known to the person skilled in the art and can generally be used again for the hydroformylation.
- the catalysts described above can also be suitably, e.g. B. by linking via functional groups suitable as anchor groups, adsorption, grafting, etc. to a suitable carrier, for. B. made of glass, silica gel, synthetic resins, etc., immobilized. They are then also suitable for use as solid-phase catalysts.
- ethylenically unsaturated compounds in particular those with at least one terminal double bond, can advantageously be hydroformylated using the process according to the invention at low temperatures and low pressures.
- shorter reaction times and / or smaller amounts of catalyst system, based on the substrate used, are required than would be required for the hydroformylation of the same substrate using the same catalytically active metal with other phosphorus-containing cocatalysts, such as Xantphos (see, for example, BC Botteghi et al. in J. Mol. Catal. A: Chem 2001, 175, 17, Table 2: high catalyst loading of 0.4-1 mol%).
- the process according to the invention makes it possible to hydroformylate ethylenically unsaturated compounds, in particular those having two terminal double bonds, with reaction times of less than 15 h, preferably less than 10 h, with small amounts of catalyst system used.
- isomerization of terminal double bonds to the thermodynamically more stable internal double bonds takes place only to a very small extent.
- the catalysts used are therefore distinguished by a high n selectivity, ie. H. Starting from ⁇ , ⁇ -dioefins, ⁇ , ⁇ -enals and / or ⁇ , ⁇ -dialdehydes are obtained in high yields.
- One embodiment of the present invention relates to the production of dialdehydes.
- the dialdehydes are produced batchwise. Discontinuous hydroformylation processes are known in principle to the person skilled in the art.
- the reactor is generally first let down.
- the synthesis gas released in the process and any unreacted unsaturated compounds can be reused in whole or in part, if appropriate after working up.
- the rest of the reactor consists essentially of dialdehyde, high-boiling by-products (hereinafter also referred to as high boilers) and catalyst.
- the reactor contents can be subjected to a one- or multi-stage separation, at least one fraction of which is enriched in dialdehyde being obtained.
- the separation into a fraction enriched in dialdehyde can be achieved in various ways. follow, for example by distillation, crystallization or Me bramfiltration, preferably by distillation.
- a reactor with a distillation column attached is used, so that the distillation can be carried out directly from the reactor.
- the distillation column is optionally provided with rectification trays in order to achieve the best possible separation performance.
- the distillation can be carried out at normal pressure or at reduced pressure.
- the dialdehyde-enriched fraction can be isolated at the top or in the upper region of the column, it being possible to isolate at least one dialdehyde-depleted fraction in the bottom or in the lower region of the column.
- the fraction enriched in dialdehyde can be subjected to a further purification step.
- the fraction depleted in dialdehyde essentially contains high boilers and the catalyst.
- the catalyst can be separated off by customary processes known to the person skilled in the art and can generally be used again in a further hydroformylation, if appropriate after working up.
- the dialdehydes are produced continuously.
- an unsaturated compound is subjected to hydroformylation in one or more reaction zones.
- a discharge is withdrawn from the reaction zone, which is generally first depressurized. This releases unreacted synthesis gas and unsaturated compounds, which are usually returned to the reaction zone - if necessary after working up.
- the remaining discharge can be separated into a fraction enriched in dialdehyde by means of customary measures known from the prior art, for example by distillation, crystallization or membrane filtration. Suitable distillation plants are known to the person skilled in the art. Thin film evaporators are also suitable.
- a fraction consisting essentially of high boilers and catalyst is removed from the bottom or from the lower region of the column and can be returned directly to the reaction zone.
- the high boilers are preferably discharged beforehand in whole or in part before recycling and the catalyst is returned to the reaction zone, if appropriate after working up.
- At least one fraction enriched in dialdehyde which may also contain unsaturated monoaldehyde, is removed from the top or in the upper region of the column.
- the fraction containing dialdehyde-enriched, still unsaturated monoaldehyde is expediently subjected to at least one further separation, at least one fraction containing unsaturated monoaldehyde and a fraction enriched in dialdehyde.
- the phase enriched in unsaturated monoaldehyde is returned to the reaction zone and the phase enriched in dialdehyde is discharged.
- the present invention relates to a process for the hydroformylation of compounds having at least two ethylenically unsaturated double bonds with isolation of the unsaturated monoaldehydes (enals) formed therein.
- Another object of the invention is therefore a method in which
- the process can be carried out continuously, semi-continuously or batchwise. A continuous process is preferred.
- step (i) of the process according to the invention the compound containing at least two ethylenically unsaturated double bonds is set with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst which comprises at least one complex of a metal from subgroup VIII with at least one pnicogen chelate ligand of the formula I, such as previously described, includes um.
- a hydroformylation catalyst which comprises at least one complex of a metal from subgroup VIII with at least one pnicogen chelate ligand of the formula I, such as previously described, includes um.
- step (ii) a discharge is withdrawn from the reaction zone which contains essentially unreacted polyethylenically unsaturated compounds, unsaturated monoaldehyde, dialdehyde and catalyst.
- the hydroformylation catalysts can be separated off by customary processes known to the person skilled in the art and can generally be used again for the hydroformylation.
- the reaction mixture obtained in step (i) can be separated into a fraction enriched in unsaturated monoaldehyde and a fraction depleted in unsaturated monoaldehyde by means of customary measures known from the prior art (step ii).
- the separation is preferably carried out by distillation, by crystallization or by membrane filtration.
- Suitable distillation plants include all distillation devices known to those skilled in the art for the continuous or batchwise separation of liquid mixtures.
- Thin film evaporators are also suitable. These include devices in which the mixtures to be separated are distributed onto heated surfaces by being trickled off (falling film evaporator, trickling column), centrifugal force or by specially designed wipers (wiper blade evaporator, Sambay evaporator, film truder).
- the reaction effluent from the reaction zone is generally depressurized before working up by distillation.
- the unreacted synthesis gas and unreacted olefins released can be returned to the reaction zone.
- the fraction enriched in unsaturated monoaldehydes is generally obtained as the top product.
- the fraction depleted in unsaturated monoaldehydes remaining as the bottom product can be subjected to a further separation to obtain a fraction enriched in catalyst and a fraction enriched in dialdehyde.
- the fraction enriched in dialdehyde can be discharged as a further product of value.
- the substrate recovered in the separation by distillation and the catalyst system are returned to the reactor in step (iii) and subjected to the hydroformylation again.
- FIG. 1 shows a graphical representation of Example 5.
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US10/527,635 US7145042B2 (en) | 2002-09-13 | 2003-09-12 | Method for producing dialdehydes and or ethylenically unsaturated monoaldehydes by hydroformylating ethylenically unsaturated compounds |
EP03748014A EP1539666B1 (de) | 2002-09-13 | 2003-09-12 | Verfahren zur herstellung von dialdehyden und/oder ethylenisch ungesättigten monoaldehyden durch hydroformylierung ethylenisch ungesättigter verbindungen |
JP2004537069A JP4457012B2 (ja) | 2002-09-13 | 2003-09-12 | エチレン性不飽和化合物のヒドロホルミル化によるジアルデヒドおよび/またはエチレン性不飽和モノアルデヒドの製造法 |
DE50311061T DE50311061D1 (de) | 2002-09-13 | 2003-09-12 | Verfahren zur herstellung von dialdehyden und/oder ethylenisch ungesättigten monoaldehyden durch hydroformylierung ethylenisch ungesättigter verbindungen |
AU2003267348A AU2003267348A1 (en) | 2002-09-13 | 2003-09-12 | Method for producing dialdehydes and/or ethylenically unsaturated monoaldehydes by hydroformylating ethylenically unsaturated compounds |
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2002
- 2002-09-13 DE DE10242636A patent/DE10242636A1/de not_active Withdrawn
-
2003
- 2003-09-12 CN CNA038217686A patent/CN1681760A/zh active Pending
- 2003-09-12 US US10/527,635 patent/US7145042B2/en not_active Expired - Fee Related
- 2003-09-12 KR KR1020057004239A patent/KR20050057307A/ko not_active Application Discontinuation
- 2003-09-12 AU AU2003267348A patent/AU2003267348A1/en not_active Abandoned
- 2003-09-12 JP JP2004537069A patent/JP4457012B2/ja not_active Expired - Fee Related
- 2003-09-12 EP EP03748014A patent/EP1539666B1/de not_active Expired - Lifetime
- 2003-09-12 WO PCT/EP2003/010166 patent/WO2004026803A1/de active Application Filing
- 2003-09-12 DE DE50311061T patent/DE50311061D1/de not_active Expired - Lifetime
- 2003-09-12 AT AT03748014T patent/ATE420065T1/de not_active IP Right Cessation
- 2003-09-12 ES ES03748014T patent/ES2319638T3/es not_active Expired - Lifetime
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10315975B2 (en) | 2015-07-10 | 2019-06-11 | Basf Se | Method for the hydroformylation of 2-substituted butadienes and the production of secondary products thereof, especially ambrox |
US10647651B2 (en) | 2015-10-12 | 2020-05-12 | Basf Se | Hydroformylation process for producing 1,6-disubstituted hexane derivatives |
WO2017150337A1 (ja) | 2016-03-01 | 2017-09-08 | 株式会社クラレ | ジアルデヒド化合物の製造方法 |
WO2018228879A1 (en) | 2017-06-13 | 2018-12-20 | Basf Se | Hydroformylation process for producing 1,6-hexanediol derivatives |
US10941092B2 (en) | 2017-06-13 | 2021-03-09 | Basf Se | Hydroformylation process for producing 1,6-hexanediol derivatives |
Also Published As
Publication number | Publication date |
---|---|
KR20050057307A (ko) | 2005-06-16 |
US20060052645A1 (en) | 2006-03-09 |
EP1539666B1 (de) | 2009-01-07 |
JP2005538181A (ja) | 2005-12-15 |
DE10242636A1 (de) | 2004-03-18 |
ES2319638T3 (es) | 2009-05-11 |
JP4457012B2 (ja) | 2010-04-28 |
US7145042B2 (en) | 2006-12-05 |
ATE420065T1 (de) | 2009-01-15 |
CN1681760A (zh) | 2005-10-12 |
EP1539666A1 (de) | 2005-06-15 |
DE50311061D1 (de) | 2009-02-26 |
AU2003267348A1 (en) | 2004-04-08 |
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