WO2003018192A2 - Procede de preparation de 2-propylheptanol - Google Patents
Procede de preparation de 2-propylheptanol Download PDFInfo
- Publication number
- WO2003018192A2 WO2003018192A2 PCT/EP2002/009455 EP0209455W WO03018192A2 WO 2003018192 A2 WO2003018192 A2 WO 2003018192A2 EP 0209455 W EP0209455 W EP 0209455W WO 03018192 A2 WO03018192 A2 WO 03018192A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hydrogen
- alkyl
- formula
- aryl
- cycloalkyl
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 63
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 19
- YLQLIQIAXYRMDL-UHFFFAOYSA-N propylheptyl alcohol Chemical compound CCCCCC(CO)CCC YLQLIQIAXYRMDL-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000005810 carbonylation reaction Methods 0.000 title claims abstract description 12
- 230000006315 carbonylation Effects 0.000 title claims abstract description 11
- 238000005669 hydrocyanation reaction Methods 0.000 title abstract description 22
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 102
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 92
- 239000001257 hydrogen Substances 0.000 claims abstract description 92
- 239000003446 ligand Substances 0.000 claims abstract description 86
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 125000003118 aryl group Chemical group 0.000 claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims abstract description 31
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 26
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims abstract description 26
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 19
- 238000005882 aldol condensation reaction Methods 0.000 claims abstract description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims description 93
- -1 3-methylindolyl group Chemical group 0.000 claims description 84
- 125000000217 alkyl group Chemical group 0.000 claims description 54
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 49
- 230000008569 process Effects 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 30
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 30
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 29
- 229910052698 phosphorus Inorganic materials 0.000 claims description 29
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 28
- 125000001424 substituent group Chemical group 0.000 claims description 25
- 229910052736 halogen Inorganic materials 0.000 claims description 23
- 150000002367 halogens Chemical class 0.000 claims description 23
- 125000004437 phosphorous atom Chemical group 0.000 claims description 20
- 239000010948 rhodium Substances 0.000 claims description 18
- 239000004215 Carbon black (E152) Substances 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 17
- 125000003545 alkoxy group Chemical group 0.000 claims description 15
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 150000001298 alcohols Chemical class 0.000 claims description 13
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 13
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 12
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 10
- 229910052703 rhodium Inorganic materials 0.000 claims description 10
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 10
- 125000002252 acyl group Chemical group 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- 150000001450 anions Chemical class 0.000 claims description 8
- 125000004429 atom Chemical group 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 230000000737 periodic effect Effects 0.000 claims description 7
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 125000001462 1-pyrrolyl group Chemical group [*]N1C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 125000004252 isoindol-1-yl group Chemical group [H]N1C([H])=C2C([H])=C([H])C([H])=C([H])C2=C1* 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 14
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 4
- 150000001336 alkenes Chemical class 0.000 description 40
- 150000003254 radicals Chemical class 0.000 description 35
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 29
- 0 C*c(c(*)c1*)c(*)c2c1c(Nc1c(C)c(O)c(C)c3c1c(*)c(*)c(O)c3*)c(C)c(N)c2* Chemical compound C*c(c(*)c1*)c(*)c2c1c(Nc1c(C)c(O)c(C)c3c1c(*)c(*)c(O)c3*)c(C)c(N)c2* 0.000 description 27
- 239000000047 product Substances 0.000 description 25
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 25
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 22
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 22
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 18
- 229930195733 hydrocarbon Natural products 0.000 description 16
- 150000002430 hydrocarbons Chemical class 0.000 description 16
- 150000001299 aldehydes Chemical class 0.000 description 15
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 14
- VOXZDWNPVJITMN-ZBRFXRBCSA-N 17β-estradiol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 VOXZDWNPVJITMN-ZBRFXRBCSA-N 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000011574 phosphorus Substances 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 11
- 150000007942 carboxylates Chemical class 0.000 description 11
- 229910052783 alkali metal Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 10
- 239000007858 starting material Substances 0.000 description 10
- 239000013522 chelant Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 8
- 239000004014 plasticizer Substances 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- 125000001624 naphthyl group Chemical group 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000460 chlorine Chemical group 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 125000002524 organometallic group Chemical group 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 150000003512 tertiary amines Chemical class 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 4
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical class C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 150000001340 alkali metals Chemical group 0.000 description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 4
- 235000013844 butane Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 238000006317 isomerization reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000006384 oligomerization reaction Methods 0.000 description 4
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 3
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 3
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- CFEYBLWMNFZOPB-UHFFFAOYSA-N Allylacetonitrile Natural products C=CCCC#N CFEYBLWMNFZOPB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- 150000005840 aryl radicals Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000005649 metathesis reaction Methods 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 125000004043 oxo group Chemical group O=* 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 150000003233 pyrroles Chemical class 0.000 description 3
- 150000003283 rhodium Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000010626 work up procedure Methods 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- FJJYHTVHBVXEEQ-UHFFFAOYSA-N 2,2-dimethylpropanal Chemical compound CC(C)(C)C=O FJJYHTVHBVXEEQ-UHFFFAOYSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- IGJQUJNPMOYEJY-UHFFFAOYSA-N 2-acetylpyrrole Chemical compound CC(=O)C1=CC=CN1 IGJQUJNPMOYEJY-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- BYGQBDHUGHBGMD-UHFFFAOYSA-N 2-methylbutanal Chemical compound CCC(C)C=O BYGQBDHUGHBGMD-UHFFFAOYSA-N 0.000 description 2
- JMMZCWZIJXAGKW-UHFFFAOYSA-N 2-methylpent-2-ene Chemical compound CCC=C(C)C JMMZCWZIJXAGKW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LOEBNUYIWNXXQK-UHFFFAOYSA-N N1C=CC=C1.[P] Chemical class N1C=CC=C1.[P] LOEBNUYIWNXXQK-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000010719 annulation reaction Methods 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 2
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- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 229910000335 cobalt(II) sulfate Inorganic materials 0.000 description 1
- LBFUKZWYPLNNJC-UHFFFAOYSA-N cobalt(ii,iii) oxide Chemical compound [Co]=O.O=[Co]O[Co]=O LBFUKZWYPLNNJC-UHFFFAOYSA-N 0.000 description 1
- BNGNANCNFVQZBM-UHFFFAOYSA-N cobalt;ethyl hexanoate Chemical compound [Co].CCCCCC(=O)OCC BNGNANCNFVQZBM-UHFFFAOYSA-N 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 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
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 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
- 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
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 125000004420 diamide group Chemical group 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- LXHWDUISRBUGRA-UHFFFAOYSA-N dichloro(phenoxy)phosphane Chemical compound ClP(Cl)OC1=CC=CC=C1 LXHWDUISRBUGRA-UHFFFAOYSA-N 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
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- WQABCVAJNWAXTE-UHFFFAOYSA-N dimercaprol Chemical compound OCC(S)CS WQABCVAJNWAXTE-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical class C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 1
- 238000010932 ethanolysis reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WZHKDGJSXCTSCK-UHFFFAOYSA-N hept-3-ene Chemical compound CCCC=CCC WZHKDGJSXCTSCK-UHFFFAOYSA-N 0.000 description 1
- GEAWFZNTIFJMHR-UHFFFAOYSA-N hepta-1,6-diene Chemical compound C=CCCCC=C GEAWFZNTIFJMHR-UHFFFAOYSA-N 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 125000002632 imidazolidinyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 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
- 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
- 150000007517 lewis acids Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 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 1
- 239000007788 liquid Substances 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- KJALUUCEMMPKAC-ONEGZZNKSA-N methyl (e)-pent-3-enoate Chemical compound COC(=O)C\C=C\C KJALUUCEMMPKAC-ONEGZZNKSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 150000002763 monocarboxylic acids 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
- 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
- VOKXPKSMYJLAIW-UHFFFAOYSA-N nickel;phosphane Chemical compound P.[Ni] VOKXPKSMYJLAIW-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
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 125000000160 oxazolidinyl group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-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
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- BNXZQGZGPVOMDB-UHFFFAOYSA-N phenyl(1H-pyrrol-2-yl)phosphane Chemical compound P(c1ccc[nH]1)c1ccccc1 BNXZQGZGPVOMDB-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000000746 purification Methods 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
- HSKNRVWCHUCANG-UHFFFAOYSA-N pyrrol-1-ylphosphane Chemical class PN1C=CC=C1 HSKNRVWCHUCANG-UHFFFAOYSA-N 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 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
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000009419 refurbishment 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
- 230000000630 rising effect Effects 0.000 description 1
- 229910001927 ruthenium tetroxide Inorganic materials 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
- 239000000565 sealant Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000707 stereoselective effect Effects 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
- 238000006467 substitution reaction Methods 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
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- 125000005497 tetraalkylphosphonium group Chemical group 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
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 125000001984 thiazolidinyl group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000005490 tosylate group Chemical group 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 125000001834 xanthenyl group Chemical group C1=CC=CC=2OC3=CC=CC=C3C(C12)* 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—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
- B01J31/1855—Triamide derivatives thereof
-
- 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
-
- 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
- B01J31/1865—Phosphonites (RP(OR)2), their isomeric phosphinates (R2(RO)P=O) and RO-substitution derivatives thereof
- B01J31/187—Amide derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/08—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds
- C07C253/10—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds to compounds containing carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/175—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with simultaneous reduction of an oxo group
-
- 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
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
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Definitions
- the present invention relates to a process for the preparation of 2-propylheptanol, comprising the hydroformylation of butene, an aldol condensation of the hydroformylation products thus obtained and their catalytic hydrogenation.
- the invention further relates to new catalysts for the hydroformylation step and their use.
- plasticizers are used in large quantities to modify the thermoplastic properties of a large number of products that are important on an industrial scale, such as plastics in particular, but also varnishes, coating agents, sealants, etc.
- An important class of plasticizers are the ester plasticizers, which include phthalic acid esters, trimellitic acid esters, phosphoric acid esters, etc.
- the alcohols used to prepare the ester plasticizers are generally referred to as plasticizer alcohols.
- plasticizer alcohols In order to produce ester plasticizers with good performance properties, there is a need for plasticizer alcohols with about 6 to 12 carbon atoms, which are branched to a small extent (so-called semilinear alcohols), and for corresponding mixtures thereof. These include, in particular, 2-propylheptanol and alcohol mixtures containing it.
- DE-A-100 03 482 describes an integrated process for the preparation of Cg alcohols and C ⁇ 0 alcohols from butene and butane-containing C 4 -hydrocarbon mixtures, in which, among other things, the hydrocarbon mixture is subjected to hydroformylation and the C 5 - Aldehydes subjected to an aldol condensation and subsequent catalytic hydrogenation to Cio-alcohols.
- hydroformylation of olefins with more than 2 carbon atoms leads to the formation of mixtures of isomeric aldehydes due to the possible CO addition to each of the two carbon atoms of a double bond.
- double bond isomerization can occur, ie a shift of internal double bonds to a terminal position and vice versa.
- 2-propylheptanol or alcohol mixtures With a high proportion of 2-propylheptanol by hydroformylation of butene and subsequent aldol condensation, hydroformylation can therefore easily lead not only to the formation of n-valeraldehyde but also to undesired product aldehydes, which is economically disadvantageous by the entire process.
- the hydroformylation catalyst used must selectively enable and / or allow the hydroformylation of terminal olefins (1-butene) a shift of internal double bonds to a ter-
- WO 98/42716 describes a process for the preparation of 35 2,2'-bisphosphino-1,1'-binaphthylene, the phosphorus atoms of which, in addition to a large number of other radicals, can also carry pyrrole groups.
- No. 3,816,452 describes the production of differently substituted pyrrolyl monophosphines and their use as 40 flame retardants.
- EP-A-0 754 715 describes a catalyst composition comprising a metal from transition group VIII and an alkylene-bridged di (pyrrolyl-phenyl-phosphine) and their use for the production of polyketones. Catalysts based on phosphorus-containing ligands with substituted or fused pyrrole residues are not described.
- WO 00/56451 (DE-A-199 13 352) relates to cyclic oxaphosphorines substituted on the phosphorus atom with pyrrole derivatives and the use of these ligands in catalysts for hydroformylation.
- WO-A-96/01831 describes chiral diphosphines of biheterocyclic compounds of aromatic, 5-atom heterocycles and their use in chiral catalysts for stereoselective reactions.
- the heterocyclic nuclei are linked to one another via a single bond between two ring carbon atoms.
- WO-A-99/52915 describes chiral phosphorus atom-containing ligands based on bicyclic compounds of carbocyclic and heterocyclic 5- to 6-atom compounds.
- the aromatic rings forming the bicyclus are linked to one another via a single bond between two ring carbon atoms.
- WO-A-99/52632 relates to a process for hydrocyanation using phosphorus-containing chelate ligands with 1, 1 'bisphenylene or 1, 1' bisnaphthylene backbone, in which the phosphorus atom with un- substituted pyrrole, indole or imidazole groups which are bonded to the phosphorus atom via a ring nitrogen atom.
- 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.
- hetaryl radicals can also be bound to the atom of the 5th main group.
- 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 each having a single bond to a nonaromatic 5- is linked to 8-membered carbocyclic or heterocyclic bridging group.
- the phosphorus atoms can also have, among other things, hetaryl groups as further substituents.
- DE-A-100 46 026.7 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- Has atom and at least two further heteroatoms groups bound to a xanthene-like molecular structure.
- JP-A-2002 047294 describes phosphorus chelate compounds with backbones of the biphenylene type, in which two nitrogen heterocycles are also bonded to the phosphorus atoms. They are suitable as ligands for hydroformylation catalysts. Both unsubstituted and substituted pyrrole groups integrated in fused ring systems are used as nitrogen heterocycles. This document does not show any preference for substituted pyrrol groups and those which are integrated in a fused ring system and in particular additionally substituted pyrrole groups. The use of ligands of the biphenylene type in which at least one 3-alkylindol-l-yl radical is bonded to the phosphorus atoms is not described in this document.
- German patent application P 102 05 361.8 describes phosphorus chelate compounds in which three nitrogen atoms are covalently bonded to both phosphorus atoms, which are themselves part of an aromatic ring system.
- the object of the present invention is to provide an improved process for the preparation of 2-propylheptanol.
- Another object of the invention is to provide new ligands which, when used in hydroformylation catalysts, are notable for particularly high stability under the hydroformylation conditions and / or for workup.
- the first object is achieved by a process which comprises the hydroformylation of butene, an aldol condensation of the hydroformylation products thus obtained and their subsequent catalytic hydrogenation, a complex of a metal of subgroup VIII of the periodic table being used as the hydroformylation catalyst at least one pyrrole-phosphorus compound is used as ligand. Accordingly, a process for the preparation of 2-propyl-heptanol was found in which
- R 1 , R 2 , R 3 and R 4 independently of one another for hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, WC00R a , WC00-M +, W (S0 3 ) R a , W (S0 3 ) "M + , WP0 3 (R a ) (R b ), W (P0 3 ) 2 "(M +) 2 , WNE ⁇ -E 2 , W (NE 1 E 2 E 3 ) + X", W0R a , WSR a , (CHRkCH 2 0) x R a , (CH 2 NE 1 ) x R a , (CH 2 CH 2 NE 1 ) x R a , halogen, trifluoromethyl, nitro, acyl or cyano,
- W represents a single bond, a heteroatom or a divalent bridging group with 1 to 20 bridge atoms
- R a r E 1 , E 2 , E 3 each represent the same or different radicals selected from hydrogen, alkyl, cycloalkyl or aryl,
- Rb represents hydrogen, methyl or ethyl
- ⁇ ⁇ stands for an anion equivalent and x represents an integer from 1 to 240
- R 5 and R 6 independently of one another are cycloalkyl, heterocycloalkyl, aryl or hetaryl, it being possible for one of the radicals R 5 or R 6 to also represent a divalent bridging group Y which covalently connects two identical or different ligands or formula I. , and
- a and b independently of one another denote the number 0 or 1
- step b) the hydroformylation product obtained in step a) or the n-valeraldehyde enriched in step b)
- pyrrole-phosphorus compounds in which one or more unsubstituted pyrrole groups are bonded to the phosphorus atom via their nitrogen atom tend to decompose or form undesired reaction products.
- a noticeable decomposition is already induced by visible light and / or temperatures in the room temperature range and cannot be prevented by using a protective gas.
- polymeric impurities are noticeably formed.
- the bridging group Y does not represent a group of the formula
- R 7 , R 8 'R 9 and R 10 independently of one another for hydrogen, alkyl, cycloalkyl, aryl, alkoxy, halogen, S0 3 H, sulfonate, NEE 5 , alkylene-NE 4 E 5 , trifluoromethyl, nitro, alkoxycarbonyl, Are carboxyl or cyano, in which E 4 and E 5 each represent the same or different radicals selected from hydrogen, alkyl, cycloalkyl and aryl,
- a 1 and A 2 independently of one another represent 0, S, SiR 15 R 16 , NR 15 or CR 17 R 18 , where
- R 17 and R 18 independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, or the group R 17 together with another group R 17 or the group R 18 together with another group R 18 is an intramolecular bridge group D form,
- R 19 and R 20 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 bridge,
- R 21 , R 22 , R 23 and R 24 independently of one another for hydrogen
- c 0 or 1.
- alkyl includes straight-chain and branched alkyl groups. These are preferably straight-chain or branched C 1 -C 18 -alkyl, preferably C 1 -C 2 -alkyl and particularly preferably C 1 -C 4 -alkyl and very particularly preferably C 1 -C 4 -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 , 1,2-dimethylpropyl, 1, 1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl , 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1, 1-dimethylbutyl, 2, 2-dimethylbutyl, 3,3-dimethylbutyl, 1, 1,2-trimethylpropyl, 1,2,2-trimethyl - propyl, 1-ethylbutyl, 2-ethylbutyl, l-ethyl,
- alkyl also includes substituted alkyl groups.
- Substituted alkyl radicals preferably have 1, 2, 3, 4 or 5, in particular 1, 2 or 3, substituents selected from cycloalkyl, aryl, hetaryl, halogen, NE ⁇ 2 , (NE X E 2 E 3 ) + , carboxyl, Carboxylate, -S0 3 H and sulfonate.
- cycloalkyl includes unsubstituted and substituted cycloalkyl groups.
- the cycloalkyl group is preferably a C5-C7 cycloalkyl group such as cyclopentyl, cyclohexyl or cycloheptyl.
- cycloalkyl group preferably has 1, 2, 3, 4 or 5, in particular 1, 2 or 3, substituents selected from alkyl, alkoxy or halogen.
- 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 a , C00 ⁇ M + and NE ⁇ 2 , preferably alkyl, can wear.
- heterocycloaliphatic groups are pyrrolidinyl, piperidinyl, 2,2, 6, 6-tetramethyl-piperidinyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, morpholidinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinyl, tetrahydrothydhenoluryl, tyridethyridanyl, tyridylanyl, tyridethanyl, tyranethanyl, tyranethanyl called.
- Aryl preferably represents phenyl, tolyl, xylyl, mesityl, naphthyl, anthracenyl, phenanthrenyl, naphthacenyl and in particular phenyl or naphthyl.
- Substituted aryl radicals preferably have 1, 2, 3, 4 or 5, in particular 1, 2 or 3, substituents selected from alkyl, alkoxy, carboxyl, carboxylate, trifluoromethyl, -S0 3 H, sulfonate, E ⁇ 2 , alkylene-NEiE 2 , Nitro, cyano or halogen.
- Hetaryl is preferably pyrrolyl, pyrazolyl, imidazolyl, indolyl, carbazolyl, pyridyl, quinolinyl, acridinyl, pyridazinyl, pyrimidinyl or pyrazinyl.
- Substituted hetaryl radicals preferably have 1, 2 or 3 substituents selected from alkyl, alkoxy, carboxyl, carboxylate, -S0 3 H, sulfonate, NE X E 2 , alkylene-NE 1 E 2 , trifluoromethyl or halogen.
- alkyl, cycloalkyl and aryl radicals apply accordingly to alkoxy, cycloalkyloxy and aryloxy radicals.
- the radicals NE X E 2 and NE 4 E 5 preferably represent N, N-dimethylaamino, N, N-diethylamino, N, N-dipropylamino, N, N-diisopropylamino, N, N-di-n-butylamino, N, N-di-tert-butylamino, N, N-dicyclohexylamino or N, N-diphenylamino.
- Halogen represents fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.
- 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 -CC alkanols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and tert-butanol.
- M + stands for a cation equivalent, ie for a monovalent cation or the portion of a multivalent cation corresponding to a positive single charge.
- M + stands for an alkali metal cation, such as. B. Li + , Na + or K + or for an alkaline earth metal cation, for NH + or a quaternary ammonium compound, as can be obtained by protonation or quaternization of amines.
- Alkali metal cations are preferred, in particular sodium or potassium ions.
- X- stands for an anion equivalent, ie for a monovalent anion or the portion of a polyvalent anion corresponding to a negative single charge.
- X- is preferably a carbonate, carboxylate or halide, particularly preferably Cl_ and Br_ .
- 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 fused aromatic, hydroaromatic and cyclic compounds. Condensed ring systems consist of two, three or more than three rings. Depending on the type of linkage, a distinction is made between condensed ring systems between ortho annulation, ie. H. each ring has an edge or two atoms in common with each neighboring ring, and a peri-annulation in which one carbon atom belongs to more than two rings. Preferred among the condensed ring systems are ortho-condensed ring systems.
- Suitable feedstocks for the hydroformylation are both essentially pure 1-butene and mixtures of 1-butene with 2-butene and technically obtainable C-hydrocarbon streams which contain 1-butene and / or 2 butene.
- C 4 cuts which are available in large quantities from FCC systems and from steak crackers, are preferably suitable. These consist essentially of a mixture of 1,3-butadiene, the isomeric butenes and butane.
- Suitable C -carbon streams as feed contain z. B. 50 to 99, preferably 60 to 90 mol% of butenes and 1 to 50, preferably 10 to 40 mol% of butanes.
- the butene fraction preferably comprises 40 to 60 mol% of 1-butene, 20 to 30 mol% of 2-butene and less than 5 mol%, in particular less than 3 mol%, of isobutene (based on the butene fraction).
- the so-called raffinate II which is an isobutene-depleted C 4 cut from an FCC system or a steam cracker, is used as a particularly preferred feedstock.
- Hydroformylation catalysts based on the phosphoropyrrole compounds used according to the invention as ligands advantageously have a high n-selectivity, even when using 2-butene and 2-butene-containing hydrocarbon mixtures as starting material.
- such starting materials can also be used economically in the process according to the invention, since the desired n-valeraldehyde results in good yields.
- step a) of the process according to the invention preference is given to using a compound of the general formula I in which one or two of the radicals R 1 , R 2 , R 3 and R 4 are one of the abovementioned substituents other than hydrogen and the rest are hydrogen stand.
- Compounds of the formula I which have a substituent other than hydrogen in the 2-position, 2,5-position or 3,4-position are preferred.
- the substituents R 1 to R 4 which are different from hydrogen are preferably selected independently of one another from Ci to Cs, preferably Ci to C 4 alkyl, especially methyl, ethyl, isopropyl and tert-butyl, alkoxycarbonyl, such as methoxycarbonyl, ethoxycar- bonyl, isopropyloxycarbonyl and tert-butyloxycarbonyl as well as trifluoromethyl.
- step a) of the process according to the invention preference is given to using a compound of the general formula I in which the radicals R 1 and R 2 and / or R 3 and R 4 together with the carbon atoms of the pyrrole ring to which they are attached form a condensed ring system with 1, 2 or 3 further rings. If R 1 and R 2 and / or R 3 and R 4 stand for a fused-on, ie fused ring system, 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 ⁇ 2 , alkylene-NE ⁇ 2 , trifluoromethyl, nitro, C00R a , alkoxycarbonyl, acyl and cyano.
- Fused naphthalene rings are preferably unsubstituted or have 1, 2 or 3, in particular 1 or, in the non-fused ring and / or in the fused ring 2 of the substituents previously mentioned for the fused benzene rings.
- R 3 and R 4 preferably stand for hydrogen or R 4 stands for hydrogen and R 3 stands for a substituent which is selected from Ci to Cs alkyl, preferably Ci - to C-alkyl, especially methyl, ethyl, isopropyl or tert-butyl.
- At least one of the radicals R 1 , R 2 , R 3 and / or R 4 represents a polar (hydrophilic) group, in which case, as a rule, the complex formation with a Group VIII metal water-soluble complexes result.
- the polar groups are preferably selected from C00R a , COO-M +, S0 3 R a , S0 3 ⁇ M + , NEiE 2 , alkylene-NE 1 E 2 , NE ⁇ E ⁇ X ", alkylene-NE 1 E 2 E 3 + X-, OR a , SR a , (CHR b CH 2 0) x R a or (CH ⁇ H ⁇ fE 1 )) x R a , where R a , E 1 , E 2 , E 3 , R b , M + , X ⁇ and x have the meanings given above.
- a hydroformylation catalyst which comprises at least one ligand of the formula I in which the pyrrole group of the formula which is bonded to the phosphorus atom via the pyrrolic nitrogen atom
- Alk is a -CC 4 alkyl group
- R9, R h , R 1 and R k independently of one another are hydrogen, C J -C 4 -A1- kyl, C 1 -C 4 alkoxy, acyl, halogen, trifluoromethyl, C 1 -C 4 alkoxycarbonyl or carboxyl.
- 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 5 or the substituent R 2 together with the substituent R 5 can represent a divalent group -IW-, in which
- R ⁇ , R ⁇ , R v , R ⁇ and R ⁇ independently of one another are hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, and
- W represents cycloalkyl, cycloalkoxy, aryl, aryloxy, hetaryl or hetaryloxy.
- 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 pyrrole group bonded to the phosphorus atom via the pyrrolic nitrogen atom together with R 5 is a group of the formula
- I stands for a chemical bond or for O, S, SiR ⁇ Rß, NR ⁇ or optionally substituted C ⁇ -C ⁇ o alkylene, preferably CR ⁇ R ⁇ , wherein R ⁇ , R ⁇ , R ⁇ , R and R ⁇ independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
- R 1 , R 1 ', R 2 , R 2 ', R 3 , R 3 ', R 4 and R 4 ' independently of one another for hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, WCO0R a , WCOO "M + , W (S0 3 ) R a , W (S0 3 ) -M + , WP0 3 (R a ) (R b ) f W (P0 3 ) 2 "(M + ) 2 , WNE i E 2 , W (NE 1 E 2 E 3 ) + X-, W0R a , WSR a , (CHR b CH 2 0) x R a , (CH 2 NE 1 ) x R a , (CH 2 CH 2 NE 1 ) x R, halogen, trifluor ormethyl, nitro, acyl or cyano,
- W represents a single bond, a heteroatom or a divalent bridging group with 1 to 20 bridge atoms
- R a , E 1 , E 2 , E 3 are each the same or different radicals selected from hydrogen, alkyl, cycloalkyl or
- R b represents hydrogen, methyl or ethyl
- x represents an integer from 1 to 240
- R 1 and R 2 and / or R 1 'and R 2 ' together with the carbon atoms of the pyrrole ring to which they are attached can also represent a condensed ring system with 1, 2 or 3 further rings.
- I is preferably a chemical bond or a C 1 -C 8 -alkylene group, particularly preferably a methylene group.
- the compound of general formula I is preferably selected from compounds of general formulas I.1 to 1.4
- R 1 , R 2 'R 3 ' R 4 'Y, a and b have the meanings given above and
- R 5 and R 6 independently of one another represent cycloalkyl, heterocycloalkyl, aryl or hetaryl.
- R 1 to R 4 are preferably all hydrogen.
- R 1 and R 4 are preferably hydrogen and R 2 and R 3 are selected from Ci to Cs alkyl, preferably Ci to C alkyl, such as methyl, ethyl, isopropyl and tert-butyl.
- R 1 , R 2 , R 3 and R 4 are preferably selected independently of one another from Ci-Cg-alkyl, preferably C ⁇ -C 4 alkyl, such as methyl, ethyl, isopropyl and tert-butyl.
- the compound of general formula I is preferably selected from compounds of general formulas 1.5 or 1.6
- R 2 and R 3 have the meanings given above, where at least one of the radicals R 2 or R 3 is not hydrogen,
- R 5 and R 6 independently of one another represent cycloalkyl, heterocycloalkyl, aryl or hetaryl.
- the radicals R 2 and R 3 are preferably selected from C 1 -C 6 -alkyl, particularly preferably C 1 -C 4 -alkyl, such as methyl, ethyl, isopropyl and tert-butyl, and C00R a , in which R a for C 1 -C 4 alkyl, such as methyl, ethyl, isopropyl and tert-butyl.
- the ligands of the formula I are monodentate ligands.
- the radicals R 5 and R 6 are independently selected from cycloalkyl, heterocycloalkyl, aryl and hetaryl, preferably from aryl and hetaryl.
- R 5 and R 6 preferably represent optionally substituted phenyl radicals.
- R 5 furthermore preferably represents an optionally substituted phenyl radical and
- R 6 represents an optionally substituted hetaryl radical.
- the hetaryl radicals are preferably selected from radicals of the general formula III
- R 1 , R 2 , R 3 and R 4 are defined as described above, at least one of the radicals not being hydrogen.
- the ligands of the general formula I are bidentate ligands.
- one of the radicals R 5 or R 6 stands for a divalent bridging group Y which covalently connects two identical or different ligands of the formula I.
- the bridging group Y is preferably selected from groups of the formulas II. A to II.t.
- R 1 to R XI1 independently of one another represent hydrogen, alkyl, cycloalkyl, aryl, alkoxy, halogen, S0 3 H, sulfonate, NEE 5 , alkylene-NE 4 E 5 , trifluoromethyl, nitro, alkoxycarbonyl, carboxyl or cyano, in which E 4 and E 5 each denote the same or different radicals selected from hydrogen, alkyl, cycloalkyl and aryl,
- Z represents O, S, NR 15 or SiR 15 R 16 , where R 15 and R 16 independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, or Z represents a C 1 -C 4 -alkylene bridge which can have a double bond and / or an alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl substituent,
- Z represents a C 2 -C alkylene bridge which is interrupted by O, S or NR 15 or SiR 15 R 16 ,
- one of the radicals R 1 to R IV can also represent oxo or a ketal thereof.
- the bridging group Y is preferably selected from groups of the formulas II.1 to II.5
- R 7 , R 8 'R 9 ' R 10 'R 11 ' R 12 'R 13 and R 14 independently of one another for hydrogen, alkyl, cycloalkyl, aryl, alkoxy, halogen, S0 3 H, sulfonate, NE 4 E 5 , alkylene -NE 4 E 5 , trifluoromethyl, nitro, alkoxycarbonyl, carboxyl or cyano, in which E 4 and E 5 each represent the same or different radicals selected from hydrogen, alkyl, cycloalkyl and aryl,
- Z represents 0, S, NR 15 or SiR 15 R 16 , where R 15 and R 16 independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
- Z represents a Ci to C 3 alkylene bridge which can have a double bond and / or an alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl substituent, or Z represents a C 2 -C alkylene bridge which is interrupted by 0, S or NR 15 or SiR 15 R 16 ,
- R 7 , R 8 , R 9 and R 10 generally represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl and hetaryl.
- R 7 and R 9 are preferably hydrogen and R 8 and R 10 are C ⁇ ⁇ to C 4 alkyl, such as. B. methyl, ethyl, n-propyl, n-butyl or tert-butyl. It goes without saying that the positions of the phenyl rings of the bridging group Y which are not occupied by substituents bear a hydrogen atom.
- the substituents R 7 , R 8 , R 9 and R 10 are preferably hydrogen.
- R 7 and / or R 9 stand for a fused-on, ie fused, ring system, it is 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-NE 1 E 2 , Trifluoromethyl, nitro, COOR 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.
- Y is preferably a group of the formula II.
- R 1 and R IV independently of one another are C ⁇ -C alkyl or -CC 4 alkoxy.
- R 1 and R IV are preferably selected from methyl, ethyl, isopropyl, tert-butyl and methoxy.
- R 11 and R 111 are preferably hydrogen.
- Y is preferably a group of the formula II.b, in which R IV and R v independently of one another are C ⁇ -C-alkyl or C ⁇ -C-alkoxy.
- R IV and R v are preferably selected from methyl, ethyl, isopropyl, tert-butyl and methoxy.
- R 1 , R 11 , R 1 ", R Vi , R VI m and R v m are preferably hydrogen.
- Y is furthermore preferably a group of the formula II.b, in which R 1 and R VI11 independently of one another are C ⁇ -C 4 -alkyl or C ⁇ -C 4 -alkoxy. R 1 and R VI11 are particularly preferably tert-butyl. In these compounds R ", R 111 , R IV , R v , R VI , R VI1 are particularly preferably hydrogen. Furthermore, in these compounds R 111 and R VI are independently of one another Cein-C 4 -alkyl or C ⁇ -C 4 alkoxy, R 111 and R VI are particularly preferably selected independently of one another from methyl, Ethyl, isopropyl, tert-butyl and methoxy.
- Y is furthermore preferably a group of the formula II.
- R 11 and R VI1 are hydrogen.
- R 1 , R 111 , R IV , R v , R VI and R VI11 are preferably, independently of one another, C ⁇ -C 4 -alkyl or C ⁇ -C-alkoxy.
- R 1 , R 111 , R IV , R v , R VI and R VI11 are particularly preferably selected independently of one another from methyl, ethyl, isopropyl, tert-butyl and methoxy.
- Y is furthermore preferably a group of the formula II.c, in which Z represents a C ⁇ -C 4 -alkylene group, in particular methylene.
- R IV and R v are preferably, independently of one another, C ⁇ -C 4 -alkyl or C ⁇ -C 4 -alkoxy.
- R IV and R v are particularly preferably selected independently of one another from methyl, ethyl, isopropyl, tert-butyl and methoxy.
- the radicals R 1 , R 11 , R 111 , R VI , R VI1 and R VI11 are preferably hydrogen.
- Y preferably represents a group of the formula II.c, in which Z represents a C ⁇ -C alkylene bridge which has at least one alkyl, cycloalkyl or aryl radical. Z particularly preferably represents a methylene bridge which has two C ⁇ -C-alkyl radicals, in particular two methyl radicals.
- the radicals R 1 and R VI11 are preferably independently of one another C ⁇ -C 4 -alkyl or C ⁇ -C 4 -alkoxy. R 1 and R VI11 are particularly preferably selected independently of one another from methyl, ethyl, isopropyl, tert-butyl and methoxy.
- Y is further preferably a group of the formula II.d, in which R 1 and R XI1 independently of one another are C ⁇ -C 4 -alkyl or C ⁇ -C 4 -alkoxy.
- R 1 and R XI1 are independently selected from methyl, ethyl, isopropyl, tert-butyl and methoxy.
- the radicals R 11 to R XI are particularly preferably hydrogen.
- Y preferably represents a group of the formula II.e, in which R 1 and R XI1 independently of one another are C ⁇ -C 4 -alkyl or C ⁇ -C-alkoxy.
- R 1 and R XI1 are independently selected from methyl, ethyl, isopropyl, tert-butyl and methoxy.
- the radicals R 11 to R XI are particularly preferably hydrogen.
- Y is furthermore preferably a group of the formula II.
- Z is a C ⁇ -C 4 -alkylene group which has at least one alkyl, cycloalkyl or aryl substituent.
- Z particularly preferably represents a methylene group which has two C ⁇ -C-alkyl radicals, especially two methyl radicals.
- the radicals R 1 and R VI11 are particularly preferably independent from each other for C ⁇ -C 4 alkyl or C ⁇ -C-alkoxy.
- R 1 and R VI11 are selected independently of one another from methyl, ethyl, isopropyl, tert-butyl and methoxy.
- the radicals R 11 , R 111 , R IV , R v , R VI and R VI1 are preferably hydrogen.
- Y is furthermore preferably a group of the formula II.g, in which R 1 , R 11 and R 111 are hydrogen.
- Y preferably represents a group of the formula II.g, in which the ring carbon atom which carries the R 11 radical does not bear an additional hydrogen atom but an oxo group or a radical thereof and R 1 and R 111 represent hydrogen ,
- Y is furthermore preferably a group of the formula II.h, in which R 1 , R 11 and R 111 are hydrogen.
- Y preferably represents a group of the formula II.h, in which the ring carbon atom which carries the R 11 radical does not bear an additional hydrogen atom but an oxo group or a radical thereof and R 1 and R 111 represent hydrogen ,
- Y is furthermore preferably a group of the formula II.i in which R 1 , R 11 , R 111 and R IV are hydrogen.
- Y is furthermore preferably a group of the formula II.k, in which R 1 , R 11 , R 111 and R IV stand for hydrogen.
- Y preferably represents a group of the formula II.1, in which R 1 , R 11 , R 111 and R IV stand for hydrogen.
- Y preferably represents a group of the formula II.m, in which R 1 , R 11 , R 111 and R IV stand for hydrogen.
- Y is furthermore preferably a group of the formula II.n, where R 1 , R 11 , R 111 and R IV are hydrogen.
- Y is furthermore preferably a group of the formula II.n, in which one of the radicals R 1 to R IV is C ⁇ -C 4 -alkyl or C ⁇ -C-alkoxy. At least one of the radicals R 1 to R IV is then particularly preferably methyl, ethyl, isopropyl, tert-butyl or methoxy.
- Y is furthermore preferably a group of the formula II.o in which R 1 , R 11 , R 111 and R IV are hydrogen.
- Y further preferably represents a group of the formula II.o, in which one of the radicals R i , R 11 , R i n or R IV represents C ⁇ -C 4 -alkyl or C ⁇ -C 4 -alkoxy.
- R 1 to R IV are methyl, ethyl, tert-butyl or methoxy.
- Y is furthermore preferably a group of the formula II.p, in which R 1 and R VI independently of one another are C ⁇ -C 4 -alkyl or C ⁇ -C 4 -alkoxy. R 1 and R VI are particularly preferably selected independently of one another from methyl, ethyl, isopropyl, tert-butyl and methoxy. In these compounds, R 11 , R 111 , R IV and R v are particularly preferably hydrogen. In addition, preferably in the compounds II.p R 1 , R 111 , R IV and R VI independently of one another are C ⁇ -C 4 -alkyl or C ⁇ -C 4 -alkoxy. R 1 , R 111 , R IV and R VI are then particularly preferably selected independently of one another from methyl, ethyl, isopropyl, tert-butyl and methoxy.
- Y is furthermore preferably a group of the formula II.q, where R 1 and R VI independently of one another are C ⁇ -C 4 -alkyl or
- R 1 and R VI are particularly preferably selected independently of one another from methyl, ethyl, isopropyl, tert-butyl and methoxy.
- R 11 , R 111 , R IV and R v are particularly preferably hydrogen.
- R 111 and R IV are independently C ⁇ -C 4 -alkyl or C ⁇ -C-alkoxy.
- RIII and RIV are then particularly preferably selected independently of one another from methyl, ethyl, isopropyl, tert-butyl and methoxy.
- Y preferably represents a group of the formula II.r, II.s or Il.t, where Z represents CH 2 , C 2 H 2 or C 2 H.
- the monodentate phosphoropyrrole compounds of the general formula I used according to the invention can be prepared, for example, according to the following scheme 1:
- R 1 , R 2 , R 3 , R 4 , R 5 and R 6 have the meaning given above.
- the bidentate phosphoropyrrole compounds of the formula I used according to the invention can be prepared analogously to Scheme 1, starting from compounds L 1 - (0) b -Y- (0) a -L 1 .
- the preparation of compounds of the formula II.2 can start from compounds of the formula II.2a
- Butyllithium or the like subsequent reaction with a borane such as B (OCH 3 ) 3 or B (OCH (CH 3 ) 2 ) 3 and oxidation of the diborane compound formed in this way with a peroxide, preferably hydrogen peroxide in the presence of aqueous alkali metal hydroxide, preferably lithium -, sodium or potassium hydroxide can be obtained.
- a borane such as B (OCH 3 ) 3 or B (OCH (CH 3 ) 2 ) 3
- a peroxide preferably hydrogen peroxide in the presence of aqueous alkali metal hydroxide, preferably lithium -, sodium or potassium hydroxide
- the starting compounds of the general formula II.2a are advantageously combined with a halogen compound of the formula HalPX 1 ((0) a R 5 ) and
- HalPX 1 ((0) b R 6 ) in the presence of a base.
- Shark is preferably chlorine or bromine.
- the compounds HalPX ⁇ (0) a R 5 ) and HalPX ⁇ (0) b R 6 ) can, for example, in analogy to the method of Petersen et al, J. Am. Chem. Soc. 117, 7696 (1995) by reacting the substituted and / or fused pyrrole compound in question with the phosphorus trihalide in question, e.g. B. phosphorus trichloride, in the presence of a tertiary amine, e.g. B. triethylamine, are obtained, the stoichiometry of this reaction being observed. In analogy to this procedure, e.g. B.
- HalPX 1 ((0) a R 5 ) and HalPX 1 ((0) b R 6 ) are obtainable.
- So z. B. by reacting phenol with phosphorus trichloride in the presence of a tertiary amine, e.g. As triethylamine, the phenoxyphosphorus dichloride are generated, which after reaction with an equivalent of the pyrrole compound in question, for. B. pyrrole, in the presence of a tertiary amine, phenoxy-pyrrolyl-phosphorus chloride.
- the 2,2'-bisindole starting compounds can be prepared analogously to Tetrahedron 51, 5637 (1995) and Tetrahedron 51, 12801 (1995), and the bis-2, 2'-pyrrolyl-methanes can be prepared in accordance with the information given by J . Org. Chem. 64/1391 (1999) and the preparation of the 2 'pyrrolyl-o-phenoxy-methane according to J. Org. Chem. 16, 5060 (1981).
- the reaction of these compounds with the compounds HalPX 1 ((0) a R 5 ) and HalPX 1 ((0) b R 6 ) in the presence of a base, preferably a tertiary amine, such as triethylamine, or an alkali metal or alkaline earth metal hydride, for example sodium hydride, potassium hydride or calcium hydride, directly to those according to the invention Picnicogen chelate compounds of the general formula I with a, b 0.
- 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 is a metal of subgroup VIII, G is a phosphorus-containing ligand of the formula I and d, e, f, g are integers, depending on the valency and type of the metal and the binding 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 according to the invention can, if desired, additionally comprise at least one further non-inventive ligand, for example from the class of triarylphosphines, especially triphenylphosphine, triarylphosphites, triarylphosphinites, triarylphosphonites, phosphabenzenes, trialkylphosphines or phosphametallocenes.
- Such complexes of the metal Z with ligands according to the invention and not according to the invention are formed, for example, in an equilibrium reaction after adding a ligand not according to the invention to form a complex of the general formula H g Z a (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 invention can also be prepared separately and isolated by customary processes. To prepare the catalysts according to the invention in situ, at least one compound of the general formula I, a compound or a complex of a metal from subgroup VIII, if desired one or more additional ligands not according to the invention and optionally an activating agent in an inert solvent the hydroformylation implement conditions.
- 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, rhodium (II) - and rhodium ( III) carboxylate, rhodium (II) and rhodium (III) acetate, rhodium (III) oxide, salts of rhodium (III) acid, trisammonium hexachlororhodate (III) etc.
- rhodium (II) and rhodium (III) salts such as rhodium (III) chloride, rhodium (III) nitrate, rhodium (III) sulfate, potassium rhodium sulfate
- 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 K 2 Ru0 or KRu0 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 partly 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, cobalt naphthenoate, and the cobalt caprolactamate Complex
- the carbonyl complexes of cobalt such as dicobalt octacarbonyl, tetrakobalt dodecacarbonyl and hexacobalt hexadecacarbonyl can also be used here.
- Suitable activating agents are e.g. B. Brönsted acids, Lewis acids, such as. B. BF 3 , A1C1 3 , ZnCl, and Lewis bases.
- the solvents used are preferably the aldehydes which are formed in the hydroformylation of the respective olefins, and also their higher-boiling secondary reaction products, for. B. the products of aldol condensation.
- 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 alkano len, for example ethyl acetate 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. So-called “ionic liquids” can also be used as solvents.
- liquid salts for example N, N'-di-alkylimidazolium 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 such as the trishexyl (tetra-decyl) phosphonium salts, for example the tetrafluoroborates, acetates, tetrachloroaluminates, hexafluorophosphates, chlorides and tosylates.
- N, N'-di-alkylimidazolium salts such as the N-butyl-N'-methylimidazolium salts
- tetraalkylammonium salts such as the tetra-n-buty
- the reactions are then carried out in 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.
- the molar ratio of compound I to subgroup VIII metal 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 ,
- 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 ed., 1951, pp. 743 ff.
- 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, if desired, with a stirring device and can be provided with an inner lining.
- composition of the synthesis gas of carbon monoxide and hydrogen used in the process according to the invention can vary in wide ranges.
- the molar ratio of carbon monoxide and hydrogen is usually about 1:99 to 80:20, 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 the range from about 20 to 180 ° C., preferably about 50 to 150 ° 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 according to the invention used.
- the catalysts according to the invention based on phosphorus-containing compounds allow reaction in a range of low pressures, such as in the range from 1 to 100 bar.
- hydroformylation catalysts used according to the invention and the hydroformylation catalysts according to the invention 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 product-enriched fraction obtained in step a) after separation of the catalyst system is subjected to a further separation in order to obtain a fraction enriched in n-valeraldehyde.
- the hydroformylation product is separated into an n-valeraldehyde-enriched fraction and an n-valeraldehyde-depleted fraction by conventional methods known to those skilled in the art. Distillation using known separation apparatuses, such as distillation columns, e.g. B. tray columns, which can be equipped with bells, sieve plates, sieve trays, valves etc. if desired, evaporators, such as thin-film evaporators, falling film evaporators, wiper blade evaporators etc. c) aldol condensation
- Two molecules of C 5 aldehyde can be condensed to form ⁇ , ⁇ -unsaturated C ⁇ 0 aldehydes.
- the aldol condensation takes place in a manner known per se, for. B. by the action of an aqueous base such as sodium hydroxide solution or potassium hydroxide solution.
- a heterogeneous basic catalyst such as magnesium and / or aluminum oxide, can also be used (see, for example, EP-A 792 862).
- the condensation of two molecules of n-valeraldehyde results in 2-propyl-2-heptenal.
- step a) or after the separation in step b) also has other C 5 aldehydes, such as 2-methylbutanal and, if appropriate, 2,2-dimethylpropanal, these likewise undergo aldol condensation, in which case the condensation products of all possible aldehyde combinations result, for example 2-propyl-4-methyl-2-hexenal.
- the products of the aldol condensation may by hydrogen catalytically to C ⁇ 0 alcohols, such as especially 2-propylheptanol, be driert hy-.
- the catalysts of the hydroformylation are generally also suitable at higher temperatures; in general, however, more selective hydrogenation catalysts are preferred, which are used in a separate hydrogenation stage.
- Suitable hydrogenation catalysts are generally transition metals, such as. B. Cr, Mo, W, Fe, Rh, Co, Ni, Pd, Pt, Ru etc. or mixtures thereof, which increase the activity and stability on supports such. B. activated carbon, aluminum oxide, diatomaceous earth, etc. can be applied.
- Fe, Co and preferably Ni also in the form of the Raney catalysts, can be used as a metal sponge with a very large surface area.
- the hydrogenation of the C ⁇ o-aldehydes takes place depending on the activity of the catalyst, preferably at elevated temperatures and elevated pressure.
- the hydrogenation temperature is preferably about 80 to 250 ° C., the pressure is preferably about 50 to 350 bar.
- the crude hydrogenation product can by conventional methods, e.g. B. by distillation to the C 10 alcohols. e) separation
- the hydrogenation products can be subjected to a further separation to obtain a fraction enriched in 2-propylheptanol and a fraction depleted in 2-propylheptanol.
- This separation can be carried out by customary methods known to those skilled in the art, such as, for. B. by distillation.
- Hydroformylation catalysts which have a complex of at least one metal from subgroup VIII of the periodic table and which have at least one pyrrole phosphorus compound of the general formula I with substituted and / or fused pyrrole skeleton as ligands are advantageously suitable for use in a process for the preparation of 2-propylheptanol.
- the catalysts have a high n-selectivity, so that both when using essentially pure 1-butene and when using l-butene / 2-butene-containing hydrocarbon mixtures, such as C-cuts, a good yield of n- Valeraldehyde is obtained.
- the catalysts used according to the invention are also suitable for double bond isomerization from an internal to a terminal position, so that n-valeraldehyde is obtained in good yields even when using 2-butene and higher concentrations of hydrocarbon mixtures containing 2-butene ,
- the catalysts used according to the invention based on substituted or fused pyrrole skeletons show essentially no decomposition under the hydroformylation conditions, ie. H. in the presence of aldehydes.
- the invention furthermore relates to catalysts comprising complexes with a metal of subgroup VIII of the Periodic Table of the Elements, which contain at least one compound of the formula I, as described above, as ligands, with the exception of compounds of the formula
- R, R d , R e , R f (1-indolyl)
- R c , R e (1-indolyl)
- R, R d , R e , R f (1-indolyl)
- R c , R ⁇ (1-indolyl);
- R d , Rf ;
- Phenyl c: R c , Re (i- indolyl);
- R d , R f (1-pyrrolyl) d:
- R c , Re (i- indolyl);
- R, R (O-phenyl);
- R 1 , R 111 , R IV , R v , R VI and R VI11 represent substituents other than hydrogen and
- R 1 , R 111 , R VI and R VI11 represent substituents other than hydrogen and
- R 1 , R 2 , R 3 and R 4 have the meanings given in claim 1.
- catalysts comprising complexes with a metal of subgroup VIII of the Periodic Table, which have as ligands at least one compound of the formula I, as defined above, in which in at least one of the groups of the formula
- radicals R 3 and R 4 are selected independently of one another from C ⁇ -C-alkyl radicals, in particular from methyl, ethyl, isopropyl and tert-butyl.
- These catalysts preferably have 2, 3 or 4 of these groups.
- Catalysts are particularly preferred, comprising complexes with a metal of subgroup VIII of the periodic table, which have as ligands at least one compound of the formula I, as defined above, in which at least one of the groups of the formula
- These catalysts preferably have 2, 3 or 4 2,3-dialkylindol-1-yl groups, such as 2,3-dimethylindol-l-yl groups.
- These catalysts preferably have 2, 3 or 4 3-alkylindol-1-yl groups, such as 3-methylindol-1-yl groups (1-skatolyl groups).
- Catalysts based on 3-alkylindol-l-yl groups are particularly stable.
- the metal of subgroup VIII is preferably selected from cobalt, rhodium, ruthenium or iridium.
- the catalysts of the invention are very generally suitable in processes for the hydroformylation of compounds which contain at least one ethylenically unsaturated double bond by reaction with carbon monoxide and hydrogen.
- catalysts based on ligands which have substituted and / or pyrrole groups integrated in an annulated ring system are notable for greater stability compared to catalysts based on ligands which have unsubstituted pyrrole groups , out.
- the invention therefore furthermore relates to a process for the hydroformylation of compounds which contain at least one ethylenically unsaturated double bond by reaction with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst comprising at least one complex of a metal from subgroup VIII with at least one ligand of general formula I as previously defined.
- a hydroformylation catalyst comprising at least one complex of a metal from subgroup VIII with at least one ligand of general formula I as previously defined.
- all compounds which contain one or more ethylenically unsaturated double bonds are suitable as substrates for the hydroformylation process according to the invention.
- These include e.g. B. olefins, such as ⁇ -olefins, internal straight-chain and internal branched olefins.
- Suitable ⁇ -olefins are e.g. B. propene, 1-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, allyl alcohols etc.
- Suitable branched, internal olefins are preferably C to C 20 olefins, such as 2-methyl-2-butene, 2-methyl-2-pentene, 3-methyl-2-pentene, branched, internal heptene mixtures, branched, internal Octene mixtures, branched, internal non-mixtures, branched, internal decene mixtures, branched, internal undecene mixtures, branched, internal dodecene mixtures etc.
- Suitable olefins to be hydroformylated are also C 5 bis
- Cg-cycloalkenes such as cyclopentene, cyclohexene, cycloheptene, cyclooctene and their derivatives, such as. B. whose C ⁇ ⁇ to C 20 alkyl derivatives with 1 to 5 alkyl substituents.
- Suitable olefins to be hydroformylated are also vinyl aromatics, such as styrene, ⁇ -methylstyrene, 4-isobutylstyrene etc.
- Suitable olefins to be hydroformylated are furthermore ⁇ , ⁇ -ethylenically unsaturated mono- and / or dicarboxylic acids, their esters, half-esters and amides, such as acrylic acid , Methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, 3-pentenoic acid methyl ester, 4-pentenoic acid methyl ester, oleic acid methyl ester, acrylic acid methyl ester, methacrylic acid methyl ester, unsaturated nitriles, such as 3-pentenenitrile, 4-pentenenitrile ether, acrylonitrile ether, acrylonitrile ether, acrylonitrile ether Vinyl ethyl ether, vinyl propyl ether etc., C ⁇ ⁇ to C 2 Q-alkenols, -alkenediols and -alkadienols, such as 2,7-octadie
- Suitable substrates are further di- or polyenes with isolated or conjugated double bonds. These include e.g. B. 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1, 7-0ctadiene, vinylcyclohexene, dicyclopentadiene, 1,5,9-cyclooctatriene and butadiene homo- and copolymers.
- the unsaturated compound used for the hydroformylation is preferably selected from internal linear olefins and olefin mixtures which contain at least one internal linear olefin.
- Suitable linear (straight-chain) internal olefins are preferably C to C 2 o-01efins, such as 2-butene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, 3-heptene, 2-octene, 3-0ctene , 4-0cten etc. and mixtures thereof.
- preference is given to using an industrially accessible olefin mixture which in particular contains at least one internal linear olefin. These include e.g. B.
- the Ziegler olefins obtained by targeted ethene oligomerization in the presence of alkyl aluminum catalysts are essentially unbranched olefins with a terminal double bond and an even number of carbon atoms.
- These also include the olefins obtained by ethene oligomerization in the presence of various catalyst systems, e.g. B. the predominantly linear ⁇ -olefins obtained in the presence of alkyl aluminum chloride / titanium tetrachloride catalysts and the ⁇ -olefins obtained in the presence of nickel-phosphine complex catalysts according to the Shell Higher Olefin Process (SHOP).
- SHOP Shell Higher Olefin Process
- Suitable technically accessible olefin mixtures are still used in the paraffin dehydrogenation of corresponding petroleum fractions, e.g. B. the so-called petroleum or diesel oil fractions obtained.
- Essentially three processes are used to convert paraffins, primarily n-paraffins to olefins:
- Thermal cracking leads predominantly to ⁇ -olefins, while the other variants result in olefin mixtures which generally also have relatively large proportions of olefins with an internal double bond.
- Suitable olefin mixtures are furthermore the olefins obtained in metathesis or telomerization reactions. These include e.g. B. the olefins from the Phillips-triolefin process, a modified SHOP process from ethylene oligomerization, double bond isomerization and subsequent metathesis (ethanolysis).
- Suitable technical olefin mixtures which can be used in the hydroformylation process according to the invention are furthermore selected from dibutenes, tributenes, tetrabutenes, dipropenes, tripropenes, tetrapropenes, mixtures of butene isomers, in particular raffinate II, dihexenes, dimers and oligomers from the Dimersol® process from IFP, Octolprocess® from Hüls, Polygas® process etc.
- 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, a compound or a complex of a metal from subgroup VIII and optionally an activating agent in an inert solvent the hydroformylation conditions to react.
- the catalysts according to the invention described above which comprise chiral compounds of the general formula I, are suitable for enantioselective hydroformylation.
- the catalysts described above can also be suitably, e.g. B. by connection 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.
- the catalysts prepared from the compounds of general formula I according to the invention not only have a high activity with regard to the hydroformylation of terminal olefins, but also with respect to the isomerizing hydroformylation of olefins with internal double bonds to give aldehyde products with high linearity.
- the olefins are hydrogenated only to a very small extent.
- Another object of the invention is the use of catalysts comprising at least one complex of a metal of subgroup VIII with at least one compound of the general formula I, as described above, for hydroformylation, hydrocyanation, carbonylation and for hydrogenation.
- the hydrocyanation of olefins represents a further area of use for the catalysts according to the invention.
- the hydrocyanation catalysts according to the invention also comprise complexes of a metal of subgroup VIII, in particular cobalt, nickel, ruthenium, rhodium, palladium, platinum, preferably nickel, palladium and platinum and all particularly preferably nickel.
- the metal in the metal complex according to the invention is zero-valued.
- the metal complexes can be prepared as previously described for use as hydroformylation catalysts. The same applies to the in situ production of the hydrocyanation catalysts according to the invention.
- a suitable nickel complex for the preparation of a hydrocyanation catalyst is e.g. B. Bis (1,5-cyclooctadiene) nickel (0).
- hydrocyanation catalysts analogous to the process described for the hydroformylation catalysts drive, be made in situ.
- the invention therefore furthermore relates to a process for the preparation of nitriles by catalytic hydrocyanation, in which the hydrocyanation takes place in the presence of at least one of the catalysts according to the invention described above.
- Suitable olefins for hydrocyanation are generally the olefins previously mentioned as starting materials for hydroformylation.
- a special embodiment of the method according to the invention relates
- a hydrocarbon mixture is preferably used which has a 1,3-butadiene content of at least 10% by volume, preferably at least
- 1,3-butadiene-containing hydrocarbon mixtures are available on an industrial scale. So z. B. when working up oil by steam cracking naphtha as a C-cut
- hydrocarbon mixture with a high total olefin content, with about 40% being 1,3-butadiene and the rest mono-olefins and polyunsaturated hydrocarbons and alkanes.
- These streams always contain small amounts of generally up to 5% of alkynes, 1,2-dienes and vinyl
- Pure 1,3-butadiene can e.g. B. be isolated by extractive distillation from commercially available hydrocarbon mixtures.
- the catalysts of the invention can advantageously be used for the hydrocyanation of such olefin-containing, in particular 1,3-butadiene-containing, hydrocarbon mixtures, generally also without prior purification of the hydrocarbon by distillation.
- the effectiveness of the catalysts impairing olefins such as. B. alkynes or cumulenes, can optionally be removed from the hydrocarbon mixture by selective hydrogenation before the hydrocyanation. Suitable processes for selective hydrogenation are known to the specialist
- the hydrocyanation according to the invention 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, Volume 1, 3rd edition, 1951, p. 743 ff.
- a stirred tank cascade or a tubular reactor is preferably used for the continuous variant of the process according to the invention.
- Suitable, optionally pressure-resistant reactors for the semi-continuous or continuous execution are known to the person skilled in the art and are described, for. B. in Ullmann's Encyclopedia of Industrial Chemistry, Volume 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.
- hydrocyanation catalysts according to the invention can be separated from the discharge of the hydrocyanation reaction by customary processes known to the person skilled in the art and can generally be used again for the hydrocyanation.
- the invention further relates to a process for carbonylation of compounds which contain at least one ethylenically unsaturated double bond by reaction with carbon monoxide and at least one compound having a nucleophilic group in the presence of a carbonylation catalyst, in which a catalyst based on a carbonylation catalyst is used Ligands of the general formula I used.
- the carbonylation catalysts according to the invention also comprise complexes of a metal from subgroup VIII, preferably nickel, cobalt, iron, ruthenium, rhodium and palladium, in particular palladium.
- the metal complexes can be prepared as previously described for the hydroformylation catalysts and hydrocyanation catalysts. The same applies to the in situ production of the carbonylation catalysts according to the invention.
- Suitable olefins for carbonylation are the olefins which have generally been mentioned above as starting materials for hydroformylation and hydrocyanation.
- the compounds having a nucleophilic group are preferably selected from water, alcohols, thiols, carboxylic acid esters, primary and secondary amines.
- a preferred carbonylation reaction is the conversion of olefins with carbon monoxide and water to carboxylic acids (hydrocar- boxylation). This particularly includes the conversion of ethylene with carbon monoxide and water to propionic acid.
- Another object of the invention is the use of catalysts comprising a P-containing compound according to the invention, as described above, for hydroformylation, hydrocyanation, carbonylation, hydrogenation, olefin oligomerization and polymerization and for metathesis.
- Comparative ligand A was according to K.G. Moloy et al., J. Am. Chem. Soc. 117, pp. 7696-7710 (1995). The synthesis leads to
- Comparative ligand B was produced according to US 5,710,344. The synthesis leads to a clean product with a 31 P-NMR shift of +69 ppm (CeD ß ). After storing the compound under argon for 20-10 days at room temperature, a noticeable darkening was found. A 31 P NMR analysis showed a ligand degradation of 20%.
- Rh (CO) 2 acac rhodium biscarbonylacetylacetonate
- Ligand C was analogous to KG Moloy et al., J. Am. Chem. Soc. 117, pp. 7696-7710 (1995). The synthesis leads to a clean product with a 31 P NMR shift of +67 ppm (C ⁇ O). After storing the compound under argon for 3 months at room temperature, no darkening was found. Neither heating nor treatment with water led to a material change.
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Abstract
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AU2002324067A AU2002324067A1 (en) | 2001-08-24 | 2002-08-23 | Method for the production of 2-propylheptanol and hydroformylating catalysts and the further use thereof for carbonylation, hydrocyanation and hydrogenation |
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DE10141494 | 2001-08-24 | ||
DE10141494.3 | 2001-08-24 |
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WO2003018192A2 true WO2003018192A2 (fr) | 2003-03-06 |
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PCT/EP2002/009455 WO2003018192A2 (fr) | 2001-08-24 | 2002-08-23 | Procede de preparation de 2-propylheptanol |
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WO2004026803A1 (fr) * | 2002-09-13 | 2004-04-01 | Basf Aktiengesellschaft | Procede de production de dialdehydes et/ou de monoaldehydes ethyleniquement insatures par hydroformylation de composes ethyleniquement insatures |
WO2005009934A3 (fr) * | 2003-07-23 | 2005-04-07 | Basf Ag | Procede d'hydroformylation en deux etapes |
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WO2005120704A1 (fr) | 2004-06-12 | 2005-12-22 | Lg Chem. Ltd. | Composition de catalyseur contenant du phosphore et processus de d'hydroformylation faisant appel a cette composition |
WO2006045597A1 (fr) * | 2004-10-26 | 2006-05-04 | Basf Aktiengesellschaft | Ligands destines a l'hydroformulation asymetrique |
US7173138B2 (en) | 2001-03-29 | 2007-02-06 | Basf Aktiengesellschaft | Ligands for pnicogen chelate complexes with a metal of subgroup VIII and use of the complexes as catalysts for hydroformylation, carbonylation, hydrocyanation or hydrogenation |
JP2007507340A (ja) * | 2004-06-12 | 2007-03-29 | エルジー・ケム・リミテッド | 燐を含む触媒組成物及びそれを利用したヒドロホルミル化の方法 |
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CN1871066B (zh) * | 2003-10-23 | 2011-06-22 | 巴斯福股份公司 | 基于磷酰胺配体的加氢甲酰化催化剂的稳定 |
EP1755781A4 (fr) * | 2004-06-12 | 2009-05-13 | Lg Chemical Ltd | Composition de catalyseur contenant du phosphore et processus de d'hydroformylation faisant appel a cette composition |
EP1755782A4 (fr) * | 2004-06-12 | 2009-05-06 | Lg Chemical Ltd | Composition de catalyseur contenant du phosphore et procede d'hydroformylation dans lequel ladite composition est utilisee |
JP2007508131A (ja) * | 2004-06-12 | 2007-04-05 | エルジー・ケム・リミテッド | 燐を含む触媒組成物及びそれを利用したヒドロホルミル化の方法 |
JP2007507340A (ja) * | 2004-06-12 | 2007-03-29 | エルジー・ケム・リミテッド | 燐を含む触媒組成物及びそれを利用したヒドロホルミル化の方法 |
WO2005120704A1 (fr) | 2004-06-12 | 2005-12-22 | Lg Chem. Ltd. | Composition de catalyseur contenant du phosphore et processus de d'hydroformylation faisant appel a cette composition |
US8524628B2 (en) | 2004-06-12 | 2013-09-03 | Lg Chem, Ltd. | Phosphorus-containing catalyst composition and hydroformylation process using the same |
WO2006045597A1 (fr) * | 2004-10-26 | 2006-05-04 | Basf Aktiengesellschaft | Ligands destines a l'hydroformulation asymetrique |
WO2006128434A3 (fr) * | 2005-06-02 | 2007-08-30 | Studiengesellschaft Kohle Mbh | DIPHOSPHONITES CHIRAUX UTILISES EN TANT QUE LIGANDS DANS LA REDUCTION ENANTIOSELECTIVE DE CETONES, DE ß-CETO-ESTERS, DE ET CETIMINES, CATALYSEE PAR DU RUTHENIUM |
US9266808B2 (en) | 2006-11-30 | 2016-02-23 | Basf Se | Method for the hydroformylation of olefins |
WO2008065171A1 (fr) * | 2006-11-30 | 2008-06-05 | Basf Se | Procédé pour l'hydroformulation d'oléfines |
DE102008002530A1 (de) | 2007-06-28 | 2009-01-02 | Basf Se | Verfahren zur Herstellung von Alkansäureglycidestern |
US8519084B2 (en) | 2008-06-16 | 2013-08-27 | Basf Se | Use of a C11 diol or C11 diol mixture for producing polymers |
EP2740535A1 (fr) * | 2012-12-04 | 2014-06-11 | Dow Technology Investments LLC | Ligands bidentates pour hydroformylation d'éthylène |
CN104822456A (zh) * | 2012-12-04 | 2015-08-05 | 陶氏技术投资有限责任公司 | 用于氢甲酰化乙烯的双齿配位体 |
WO2014088800A1 (fr) * | 2012-12-04 | 2014-06-12 | Dow Technology Investments Llc | Ligands bidentés pour l'hydroformylation de l'éthylène |
US9795952B2 (en) | 2012-12-04 | 2017-10-24 | Dow Technology Investments Llc | Bidentate ligands for hydroformylation of ethylene |
DE102013214378A1 (de) | 2013-07-23 | 2015-01-29 | Evonik Industries Ag | Phosphoramiditderivate in der Hydroformylierung von olefinhaltigen Gemischen |
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 (fr) | 2016-03-01 | 2017-09-08 | 株式会社クラレ | Procédé de production de composé dialdéhyde |
WO2018228879A1 (fr) | 2017-06-13 | 2018-12-20 | Basf Se | Procédé d'hydroformylation pour produire des dérivés de 1,6-hexanediol |
US10941092B2 (en) | 2017-06-13 | 2021-03-09 | Basf Se | Hydroformylation process for producing 1,6-hexanediol derivatives |
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AU2002324067A1 (en) | 2003-03-10 |
WO2003018192A3 (fr) | 2003-11-13 |
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