WO2005016524A2 - Immobilisierte immidazole und ruthenium-katalysatoren - Google Patents
Immobilisierte immidazole und ruthenium-katalysatoren Download PDFInfo
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- WO2005016524A2 WO2005016524A2 PCT/EP2004/007939 EP2004007939W WO2005016524A2 WO 2005016524 A2 WO2005016524 A2 WO 2005016524A2 EP 2004007939 W EP2004007939 W EP 2004007939W WO 2005016524 A2 WO2005016524 A2 WO 2005016524A2
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- catalysts
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- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 22
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 150000002460 imidazoles Chemical class 0.000 title description 3
- -1 N,N-disubstituted imidazolium Chemical class 0.000 claims abstract description 197
- 150000001875 compounds Chemical class 0.000 claims abstract description 76
- 239000003446 ligand Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 38
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 20
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- 238000005859 coupling reaction Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 125000004432 carbon atom Chemical group C* 0.000 claims description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 229910052801 chlorine Inorganic materials 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 18
- 229930195733 hydrocarbon Natural products 0.000 claims description 18
- 229920006395 saturated elastomer Polymers 0.000 claims description 18
- 229910052794 bromium Inorganic materials 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 241000251730 Chondrichthyes Species 0.000 claims description 13
- 125000003342 alkenyl group Chemical group 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 239000007858 starting material Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 239000003622 immobilized catalyst Substances 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 125000002524 organometallic group Chemical group 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 7
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000005649 metathesis reaction Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000000741 silica gel Substances 0.000 claims description 7
- 229910002027 silica gel Inorganic materials 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000004434 sulfur atom Chemical group 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005865 alkene metathesis reaction Methods 0.000 claims description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 238000010924 continuous production Methods 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- XEMRAKSQROQPBR-UHFFFAOYSA-N (trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=CC=C1 XEMRAKSQROQPBR-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010535 acyclic diene metathesis reaction Methods 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000010923 batch production Methods 0.000 claims description 4
- 238000005686 cross metathesis reaction Methods 0.000 claims description 4
- 238000006317 isomerization reaction Methods 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000006798 ring closing metathesis reaction Methods 0.000 claims description 4
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 4
- 239000012018 catalyst precursor Substances 0.000 claims description 3
- 150000004292 cyclic ethers Chemical class 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 238000007037 hydroformylation reaction Methods 0.000 claims description 3
- 239000012429 reaction media Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 238000007341 Heck reaction Methods 0.000 claims description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 2
- 230000003100 immobilizing effect Effects 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 claims description 2
- 238000006884 silylation reaction Methods 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 229910052723 transition metal Inorganic materials 0.000 abstract description 4
- 150000003624 transition metals Chemical class 0.000 abstract description 4
- 150000001336 alkenes Chemical class 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 25
- 239000000460 chlorine Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 21
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 17
- 239000004215 Carbon black (E152) Substances 0.000 description 15
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 125000003118 aryl group Chemical group 0.000 description 13
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 13
- 150000003254 radicals Chemical group 0.000 description 13
- ATQYNBNTEXNNIK-UHFFFAOYSA-N imidazol-2-ylidene Chemical group [C]1NC=CN1 ATQYNBNTEXNNIK-UHFFFAOYSA-N 0.000 description 12
- 238000005004 MAS NMR spectroscopy Methods 0.000 description 11
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 11
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 10
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 10
- 239000012300 argon atmosphere Substances 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 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 8
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical class C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 8
- 238000011068 loading method Methods 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 125000000304 alkynyl group Chemical group 0.000 description 7
- 150000001450 anions Chemical class 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 125000000623 heterocyclic group Chemical group 0.000 description 7
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- 125000001624 naphthyl group Chemical group 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- TYMBTMOEMHDCHR-UHFFFAOYSA-M triethoxy-[3-[3-(2,4,6-trimethylphenyl)imidazol-1-ium-1-yl]propyl]silane;chloride Chemical compound [Cl-].C1=[N+](CCC[Si](OCC)(OCC)OCC)C=CN1C1=C(C)C=C(C)C=C1C TYMBTMOEMHDCHR-UHFFFAOYSA-M 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 5
- 125000002877 alkyl aryl group Chemical group 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 125000002993 cycloalkylene group Chemical group 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 125000005919 1,2,2-trimethylpropyl group Chemical group 0.000 description 4
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- GELXFVQAWNTGPQ-UHFFFAOYSA-N [N].C1=CNC=N1 Chemical compound [N].C1=CNC=N1 GELXFVQAWNTGPQ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 125000001589 carboacyl group Chemical group 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000000628 margaroyl group Chemical group O=C([*])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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 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 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- UQSGXTFHUCJKRG-UHFFFAOYSA-M trimethoxy-[4-[[3-(2,4,6-trimethylphenyl)imidazol-1-ium-1-yl]methyl]phenyl]silane;chloride Chemical compound [Cl-].C1=CC([Si](OC)(OC)OC)=CC=C1C[N+]1=CN(C=2C(=CC(C)=CC=2C)C)C=C1 UQSGXTFHUCJKRG-UHFFFAOYSA-M 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 125000006219 1-ethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 3
- JDIIGWSSTNUWGK-UHFFFAOYSA-N 1h-imidazol-3-ium;chloride Chemical compound [Cl-].[NH2+]1C=CN=C1 JDIIGWSSTNUWGK-UHFFFAOYSA-N 0.000 description 3
- 125000005916 2-methylpentyl group Chemical group 0.000 description 3
- 125000005917 3-methylpentyl group Chemical group 0.000 description 3
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 125000000392 cycloalkenyl group Chemical group 0.000 description 3
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 3
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 125000000298 cyclopropenyl group Chemical group [H]C1=C([H])C1([H])* 0.000 description 3
- 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 3
- 238000001035 drying Methods 0.000 description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000006038 hexenyl group Chemical group 0.000 description 3
- 125000005980 hexynyl group Chemical group 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 125000002883 imidazolyl group Chemical group 0.000 description 3
- 150000003949 imides Chemical class 0.000 description 3
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 3
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 3
- 229910052987 metal hydride Inorganic materials 0.000 description 3
- 150000004681 metal hydrides Chemical class 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 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 3
- 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 3
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 3
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 3
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 3
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000003568 thioethers Chemical group 0.000 description 3
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical group CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 description 2
- 125000004575 3-pyrrolidinyl group Chemical group [H]N1C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 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 2
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 125000003074 decanoyl 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(*)=O 0.000 description 2
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])* 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
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- 150000004820 halides Chemical class 0.000 description 2
- 125000000268 heptanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000006588 heterocycloalkylene group Chemical group 0.000 description 2
- 125000003104 hexanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- 150000004693 imidazolium salts Chemical class 0.000 description 2
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- 239000011261 inert gas Substances 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 125000000400 lauroyl group Chemical group O=C([*])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 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 2
- 125000001419 myristoyl group Chemical group O=C([*])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 2
- 125000001038 naphthoyl group Chemical group C1(=CC=CC2=CC=CC=C12)C(=O)* 0.000 description 2
- 125000001402 nonanoyl group Chemical group O=C([*])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 2
- 125000002801 octanoyl group Chemical group C(CCCCCCC)(=O)* 0.000 description 2
- 125000001312 palmitoyl group Chemical group O=C([*])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])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 125000004482 piperidin-4-yl group Chemical group N1CCC(CC1)* 0.000 description 2
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 2
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- 125000002948 undecyl 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])[H] 0.000 description 2
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 0 ***(CC(COC(O)=O)*1*)C1*(I)=* Chemical compound ***(CC(COC(O)=O)*1*)C1*(I)=* 0.000 description 1
- 125000005940 1,4-dioxanyl group Chemical group 0.000 description 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- 125000004484 1-methylpiperidin-4-yl group Chemical group CN1CCC(CC1)* 0.000 description 1
- 125000004214 1-pyrrolidinyl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001462 1-pyrrolyl group Chemical group [*]N1C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000006069 2,3-dimethyl-2-butenyl group Chemical group 0.000 description 1
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- 125000000069 2-butynyl group Chemical group [H]C([H])([H])C#CC([H])([H])* 0.000 description 1
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- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 description 1
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- CWDWFSXUQODZGW-UHFFFAOYSA-N 5-thiazolyl Chemical group [C]1=CN=CS1 CWDWFSXUQODZGW-UHFFFAOYSA-N 0.000 description 1
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 description 1
- 125000004648 C2-C8 alkenyl group Chemical group 0.000 description 1
- 125000004649 C2-C8 alkynyl group Chemical group 0.000 description 1
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- DDMXPIDWXIHIDX-UHFFFAOYSA-N [C].N1C=NC=C1 Chemical compound [C].N1C=NC=C1 DDMXPIDWXIHIDX-UHFFFAOYSA-N 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
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- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
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- 125000004603 benzisoxazolyl group Chemical group O1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
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- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000004230 chromenyl group Chemical group O1C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000000259 cinnolinyl group Chemical group N1=NC(=CC2=CC=CC=C12)* 0.000 description 1
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- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- ARUKYTASOALXFG-UHFFFAOYSA-N cycloheptylcycloheptane Chemical compound C1CCCCCC1C1CCCCCC1 ARUKYTASOALXFG-UHFFFAOYSA-N 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
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- 125000004572 morpholin-3-yl group Chemical group N1C(COCC1)* 0.000 description 1
- 125000000449 nitro group Chemical class [O-][N+](*)=O 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 125000002577 pseudohalo group Chemical group 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- 125000002206 pyridazin-3-yl group Chemical group [H]C1=C([H])C([H])=C(*)N=N1 0.000 description 1
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- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000003696 stearoyl group Chemical group O=C([*])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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 230000008961 swelling Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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- 125000005369 trialkoxysilyl group Chemical group 0.000 description 1
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- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 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
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
-
- 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
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
- B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
- B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2269—Heterocyclic carbenes
- B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
-
- 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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
-
- 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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
- C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
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- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
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Definitions
- the invention relates to the process for the preparation of N, N-disubstituted imidazolium salts, N-heterocyclic carbene ligands, immobilized on inorganic oxide supports. and ruthenium catalysts with N-heterocyclic carbene ligands, i.e. Compounds of general formulas (I) and (II), compounds of general formulas (III) and (IV) and compounds of general formulas (V) and (VI).
- the invention further relates to the use of the immobilized compounds of the general formulas (I - IV) in organic, organometallic or transition metal-catalyzed synthesis and the use of the compounds of the general formulas (V) and (VI) as catalysts in organic and organometallic synthesis especially for CC coupling reactions such as olefin metathesis.
- the compounds were either immobilized directly on inorganic oxides or transferred to the corresponding surface-modified silica using a sol-gel method to form A and B.
- a and B as ligand precursors for e.g. immobilized NHC ligands (N-heterocyclic carbenes), which in turn are used as ligands in catalysts, these compounds are unsuitable because the resulting NHC ligands are not thermally stable and also tend to dimerization reactions because the carbene carbon atom is not steric is adequately shielded.
- ruthenium catalysts with N-heterocyclic carbene ligands are described, for example, in WO 00/15339, WO 00/71554, WO 99/51344, EP 0721953 and, for example, in Chem. Eur. J. 2001, 7, 3236; J. Am. Chem. Soc. 1999, 121, 2674; Organic Letters 1999, 1 (6), 953 and in J. Organomet. Chem. 2000, 606, 49.
- the compounds described can only be used as homogeneous catalysts. Since the separation of the homogeneous catalysts from the reaction products is a cost-intensive and complex process, it is of great advantage to use homogeneous catalysts which are immobilized on a support in the catalytic processes.
- Immobilization of these catalysts on inorganic oxides has Buchmeiser et al. in Angew. Chem. 2000, 112, 4062, Designed Monomers ans Polymers 2002, 5 (2,3), 325 and in Adv. Synth. Catal. 2002, 344, 712.
- the immobilization method is very complex and the catalyst is separated from the inorganic oxide by an organic copolymer, which means that it is ultimately immobilized on an organic support (C).
- the object of the present invention was to immobilize, sterically demanding imidazolium and 4,5-dihydroimidazolium salts, immobilizable N-heterocyclic carbene ligands and immobilizable ruthenium catalysts with N-heterocyclic carbene ligands on inorganic oxides.
- the immobilized imidazolium and 4,5-dihydroimidazolium salts, the immobilized N-heterocyclic carbene ligands and the immobilized ruthenium catalysts should be simple to produce, they should have high thermal stability and they should be covalently bound to the inorganic support be and are available in sufficient quantities on the support surface for application reactions. They should be firmly anchored to the surface and not show any leaching.
- RA Ar, A-Ar, A-Ar-A, Het, AHet, AHetA with a total of no more than 30 carbon atoms with A straight-chain, branched, saturated C 1 -C 2 o -alkyl radical, cycloalkyl or cycloalkyl via one or two alkyl group (s) bonded with a total of 4 - 30 carbon atoms, both in the alkyl and in the cycloalkyl radical being a CH 2 or CH group through N, NH, NA, O uhd / or S and through H atoms OA, NA 2 and / or PA 2 can be replaced,
- R3 straight-chain or branched cycloalkyl or cycloalkyl bonded via one or two alkyl group (s), Ar, AAr, AArA, Het, AHet, AHetA with a total of 4 - 30 C atoms R1 and R2 independently of one another H, Cl, Br or the meaning of R3 R4 H, Cl, Br or straight-chain, branched, saturated, mono- or polyunsaturated CrC 7 alkyl radical, where one or more H in the alkyl radical can be replaced by Z R5 A, Ar, AAr R6 and R7 H, A or Ar, where H atoms in A or Ar can be substituted by alkenyl or alkynyl radicals X, identically or differently from one another, denote anionic ligands and n is 0, 1, 2, on inorganic oxides to form the compounds of
- R, R1, R2, R3, R3 ', R4, R5, R6, R7 and X are those given above
- the compounds of the general formulas (I) to (VI) are immobilized by reacting the compounds (I) to (VI) with an inorganic metal oxide in anhydrous, inert, aprotic organic solvents.
- An alcohol ROH is formed as a by-product of the reaction.
- the products (la) to (Via) can be separated from the solvent and ROH by filtration and, if appropriate, can be purified by washing with a suitable solvent.
- the immobilization can be carried out both in a batch process and in a continuous process.
- the compounds of the general formulas (Ia) and (Ila) can be used as immobilized reaction media, immobilized ionic liquids, immobilized ligand or catalyst precursors and as immobilized catalysts in organic, organometallic and transition metal-catalyzed syntheses.
- the compounds of the general formulas (purple) and (IVa) can be used as starting materials for the preparation of immobilized N-heterocyclic carbene-metal complexes and as immobilized ligands in catalytic reactions.
- the compounds of the general formulas (Va) and (Via) can be used as immobilized catalysts in organic and organometallic synthesis. In particular, they can be used as catalysts in CC coupling reactions, hydrogenations and hydroformylation.
- the compounds of the general formulas (I) to (VI) are immobilized by reacting the compounds (I) to (VI) with an inorganic metal oxide in anhydrous, inert, aprotic organic solvents.
- the order of adding the components can be chosen arbitrarily.
- the starting compounds can be predissolved or suspended in a suitable solvent.
- Halogenated or pure hydrocarbons and cyclic ethers are preferably used as solvents.
- halogenated hydrocarbons methylene chloride, chlorobenzene or trichlorotoluene are preferably used, very preferably methylene chloride.
- pure hydrocarbons pentane, hexane, heptane, octane, decane, benzene or toluene are preferably used, very preferably heptane and toluene.
- cyclic ethers tetrahydrofuran is preferably used.
- Nitrogen or argon can serve as the protective gas atmosphere.
- the starting compounds of the general formulas (I) to (VI) are added in a 0.01-100-fold excess with respect to the active OH groups on the oxide surface, preferably in a 0.1-50-fold Excess most preferably in a 0.5 - 10-fold excess.
- the reaction can take place in a temperature range from -20 ° C to + 150 ° C, preferably from 0 ° C to +120 ° C.
- the reaction time is 30 minutes to 10 days, preferably 1 hour to 2 days and most preferably 1 hour to 1 day.
- the products (Ia) to (Via) formed can be separated off in a simple manner by filtration and, if appropriate, can be purified by washing with the abovementioned solvents and then dried.
- the immobilization according to the invention can be carried out both in a batch process and in a continuous process.
- the solutions of compounds (I) to (VI) described above are pumped through a monolithic or particulate material, the corresponding material being heated to the appropriate reaction temperature.
- the solutions from (I) to (VI) can optionally be circulated and thus flow through the monolithic or particulate material several times. The flow rates can be chosen arbitrarily.
- the functionalized carrier with the above. Washed solvents and used in application reactions.
- the oxides can also be mixed in finely divided form with solutions of the compounds of the general formulas (I) - (VI) and reacted under a protective gas atmosphere at a suitable reaction temperature.
- the individual reactants can be added in any order.
- the reactions can also be carried out in a glass apparatus equipped with a stirrer, inlet and optionally outlet, with reflux condenser or condensation cooler with outlet, if this apparatus also offers the possibility of blanketing with inert gas.
- the reactions can also be carried out in a technical installation, which is optionally made of stainless steel and other suitable inert materials and has the necessary devices for temperature control, supply and removal of the starting materials and products.
- the reactions are usually carried out in batch mode, especially if the reactions are slow. If larger quantities of the desired products of the general formulas (Ia) to (Via) are to be produced and if the starting materials to be reacted are reactive compounds, it may be expedient to carry out the reactions in a corresponding system which is suitable for continuous operation is designed.
- N-heterocyclic carbene ligands stand for 1,3-disubstituted imidazol-2-ylidenes and 1,3-disubstituted imidazolin-2-ylidenes which are derived from imidazole or 4,5-dihydroimidazole as the main body.
- the carbon atom between the two nitrogen atoms of the heterocycle is a carbene carbon atom, which is coordinated to the ruthenium atom by means of the lone pair of electrons.
- the alkylidene ligand also contains a carbene
- Carbon atoms attached to the ruthenium center Carbon atoms attached to the ruthenium center.
- the compounds (Ia) to (Via) are connected to the support surface via a spacer R, which corresponds to the hydrocarbon radical R, via which the SiR ' n (OR') 3- n group of the compounds of the general formulas (I) to ( VI) is connected to the nitrogen atom of the heterocycle.
- the spacer R accordingly has the same meanings as this hydrocarbon radical.
- n unit is a hydrocarbon radical, where n can be 0, 1 or 2, preferably 0 and 1 and very preferably 0.
- This hydrocarbon radical R 'can have different meanings regardless of the position in the molecule and can be straight-chain, unbranched (linear) , branched, saturated, mono- or polyunsaturated, cyclic (A), aromatic (Ar) or alkylaromatic (AAr, AarA), optionally mono- or polysubstituted.
- R ' is preferably a straight-chain, unbranched (linear), branched, saturated, mono- or polyunsaturated, or cyclically saturated or mono- or polyunsaturated, alkyl radical with 1 - 12 carbon atoms.
- R ' is particularly preferably a straight-chain or branched saturated alkyl radical having 1-7 C atoms, that is to say a subgroup from the alkyl group A, which is defined in more detail below.
- R 'can therefore preferably have the meanings
- R ' is very particularly preferably a CC 4 alkyl radical from the group consisting of methyl, ethyl, propyl, i-propyl, butyl, i-butyl, sec-butyl and tert-butyl.
- the SiR'n (OR ') 3 -n group is connected to the nitrogen atom of the heterocycle via a hydrocarbon radical R.
- the hydrocarbon radical R is preferably a radical with 1 to 30 carbon atoms.
- This hydrocarbon radical can be straight-chain, unbranched (linear), branched, saturated, mono- or polyunsaturated, cyclic (A), or aromatic (Ar), heterocyclic or herteroaromatic (Het) and optionally mono- or polysubstituted.
- the hydrocarbon radical R can be a radical A, Ar, A-Ar, A-Ar-A, Het, A-Het, A-Het-A, where the groups A, Ar and Het can each have the meanings given below.
- R is preferably a radical A, Ar, A-Ar, A-Ar-A with not more than 20 C atoms.
- A is preferably a straight-chain or branched, saturated C 1 -C 2 alkyl radical, or a cycloalkyl having 3 - 10 C atoms or a C 4 -C 2 o-cycloalkyl bonded via one or two alkyl groups.
- Alkylene has the same meanings as given for A, with the proviso that a further bond is linked from the alkyl to the next bond neighbor.
- A is, for example, an alkylene group selected from the group consisting of methylene (-CH 2 -), ethyl (-C 2 H 4 -), propyl (-C 3 H 6 -), isopropyl (-C 3 H 6 -), butyl (- C 4 H 8 -), isobutyl (-C 4 H 8 -), sec-butyl (-C 4 H 8 -) or tert-butyl (-C 4 H 8 -), and also pentyl (-C5H1 0 -), 1-, 2- or 3-methylbutyl (-C 5 H 10 -), 1, 1-, 1, 2- or 2,2-dimethylpropyl (-C 5 H 10 -), 1-ethylpropyl (- C 5 H 10 -), hexyl (-C 6 H 12 -), 1-, 2-, 3- or 4-M ethyl pentyl (-C 6 H ⁇ 2 -), 1, 1-, 1, 2-, 1, 3-, 2,2-, 2,
- A can also be a cycloalkylene group with 3 to 30 carbon atoms, preferably C3-C9-cycloalkylene.
- cycloalkyl can be saturated, unsaturated, optionally bound to the imidazole nitrogen and the SiR ' n (OR') n - 3 group via one or two alkyl groups in the molecule.
- One or more H atoms can also be replaced by other substituents in the cycloalkylene group.
- Cycloalkyl preferably means cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, 3-menthyl or camphor-10-yl (bicyclic terpene), decalin, bicycloheptane, these groups being attached via one or two alkyl groups in the molecule the imidazole nitrogen and the SiR ' n (OR') n-3 group can be bound.
- cycloalkyl preferably means 1, 2-cyclopropyl, 1, 2- or 1, 3-cyclobutyl, 1, 2- or 1, 3-cyclopentyl, 1, 2-, 1, 3- or 1, 4-cyclohexyl, further 1, 2-, 1, 3- or 1, 4-cycloheptyl.
- the groups mentioned can also be bonded to the second imidazole nitrogen as R3 in substituted or unsubstituted form.
- A can also be an unsaturated alkenyl or alkynyl group with 2 - 20 C atoms, which are bonded both to the imidazole nitrogen or an imidazole carbon and to the SiR ' n (OR') n - 3 group can.
- Alkenyl groups can be straight-chain, branched or cyclic C2-C30 alkenyls, preferably straight-chain, branched cyclic C2-C9 alkenyls, particularly preferably straight-chain or branched C2-C6-
- Cycloalkenyl groups can be straight-chain or branched C3-C30-cycloalkenyls, preferably C3-C9-cycloalkenyls, particularly preferably C3-C6-cycloalkenyls from the group cyclopropenyl, cyclobutenyl,
- Alkynyl groups can be straight-chain or branched C2-C30-alkynyls, preferably straight-chain or branched C2-C9-alkynyls, particularly preferably straight-chain or branched C2-C6-alkynyls from the group ethynyl, propynyl, butynyl, pentinyi or hexynyl. If alkenyl, cycloalkenyl or alkynyl are part of the hydrocarbon radical R, they of course have the same meanings with the proviso that a further bond from the alkenyl or from the alkynyl to the next bond neighbor in the molecule is linked.
- Ar is a mono- or polynuclear aromatic hydrocarbon radical with 6 - 30 C atoms, which can be substituted one or more times or unsubstituted.
- Ar is preferably a mono- or polysubstituted phenyl or naphthyl, where substituents can have the meanings of A and Ar has a total of no more than 20 C atoms.
- Aryl groups can preferably be C 6 -C 10 aryls, preferably phenyl or naphthyl.
- Alkylaryls can be -C 8 alkylaryls, preferably toluyl or mesityl.
- Ar preferably denotes substituted or unsubstituted phenyl, naphthyl, anthryl, phenanthryl, which is substituted by A, OA, CO-AOH, COOH, COOA, fluorine, chlorine, bromine, iodine, hydroxy, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, Nitro, cyano, formyl, acetyl, propionyl, trifluoromethyl, amino, methylamino, ethylamino, dimethylamino, diethylamino, benzyloxy, sulfonamido, methylthio, methylsulfinyl, methylsulfonyl, methylsulfonamido, ethylsulfonamido, propylsulfonamido, butylsulfylamyloxy, methyl sulfonamido,
- Ar preferably denotes unsubstituted, mono- or polysubstituted phenyl, and in particular preferably phenyl, o-, m- or p-tolyl, o-, m- or p-ethylphenyl, o-, m- or p-propylphenyl, o -, m- or p- Isopropylphenyl, o-, m- or p-tert-butylphenyl o-, m- or p-cyanophenyl, o-, m- or p-methoxyphenyl, o-, m- or p-ethoxyphenyl, o-, m- or p-fluorophenyl, o-, m- or p-bromophenyl, o-, m- or p-chlorophenyl, o-, m- or p-methylthiopheny
- Arylene has the same meanings as for Ar, with the proviso that a further bond is formed from the aromatic system to the next bond neighbor.
- the group labeled Het can have the following meanings:
- heterocyclic radicals can also be partially or completely hydrogenated and have the following meanings:
- Heterocycloalkylene is preferably 1, 2-, 2,3- or 1, 3-pyrrolidinyl, 1, 2-, 2,4-, 4,5- or 1, 5-imidazolidinyl, 1, 2-, 2,3-, or 1, 3-pyrazolidinyl, 2,3-, 3,4-, 4,5- or 2,5-oxazolidinyl, 1, 2-, 2,3-, 3,4- or 1,4-isoxazolidinyl , 2,3-, 3,4-, 4,5- or 2,5-thiazolidinyl, 2,3-, 3,4-, 4,5- or 2,5-isothiazolidinyl, 1, 2-, 2, 3-, 3,4- or 1, 4-piperidinyl, 1, 4- or 1, 2-piperazinyl, further preferably 1, 2,3-tetrahydro-triazoM, 2- or -1, 4-yl, 1, 2 , 4-tetrahydro-triazol-1, 2- or 3,5-yl, 1, 2- or 2,5-tetrahydro-tetrazolyl
- the hydrocarbon radical R is very particularly preferably a group with not more than 20 carbon atoms and takes on meanings selected from compounds which form the -C 1 -C 2 -alkylenes, C 3 -C ⁇ o-cycloalkylenes, or via one or two alkyl groups (n) Bound C 4 -C 20 cycloalkylenes, C 6 -C 4 -arylenes or the C 7 -C 20 alkylarylenes count and particularly preferably a CrC 4 alkylene chain from the series methylene, ethylene, propylene and butylene or a C 6 -C 8 arylene chain from the series -C 6 H 4 - and -C 6 H 2 Me 2 - or a C 7 -C 9 alkylaryl chain from the series -CH 2 C 6 H 4 -, -CH 2 C 6 H 2 Me 2 -, -CH 2 C 6 H 4 CH 2 - and - CH 2 C 6 H 2 Me 2 CH 2 -.
- R3 is a hydrocarbon radical which can assume all meanings of A, Ar, AAr, AArA, Het, AHet, AHetA, in which H atoms can be replaced by functional groups Z.
- This hydrocarbon radical can be straight-chain, unbranched (linear), branched, saturated, mono- or polyunsaturated, cyclic (A), or aromatic (Ar), heterocyclic or herteroaromatic (Het) and optionally mono- or polysubstituted.
- the hydrocarbon radical R3 is a radical which has a stabilizing effect on the carbene function of the compounds of the general formulas (I) and (II). H atoms in R3 can be replaced by functional groups Z, as defined below.
- R3 is preferably an aliphatic, aromatic or heteroaromatic hydrocarbon radical, specifically as described above, an aliphatic radical A, an aromatic hydrocarbon Ar from the groups listed above or a heterocyclic substituent Het as defined above.
- R3 is very preferably an aliphatic. H. a straight-chain, unbranched (linear), branched, saturated, mono- or polyunsaturated, or a cyclic aliphatic or aromatic hydrocarbon residue with 1 - 18 C-atoms. From this group of
- R1 and R2 can independently be H or assume all meanings of shark, A, Ar and AAr, as indicated above, where in A and Ar H atoms can be replaced by functional groups Z, and shark F, Cl, Br or I can mean.
- R1 and R2 particularly preferably assume the meanings of R3 or denote H, Cl or Br.
- R1 and R2 independently of one another denote H, Cl, Br, straight-chain, branched, saturated, mono- or polyunsaturated d- C 7 -alkyl radical , where one or more H may be replaced by Z in the alkyl radical.
- H atoms can be replaced by functional groups Z and carry N, P, O or S atoms. They can be groups which have one or more alcohol, aldehyde, carboxylic acid, amine, amide, imide, phosphine, ether or thioether function, ie they can include radicals with the meanings OA, NHA, NAA ', PAA', CN, NO 2 , SA, SOA, SO 2 A or SO 2 Ar, where A, A 'and A "can independently of one another take the meanings of A according to the given definition.
- a group Z is preferably OA, NHA, NAA ' and PAA '.
- R1 and R2 can therefore also be, for example, SO 3 H, F, Cl, a hydroxyl, alkanoyl or cycloalkanoyl radical.
- R1, R2 or R2 can mean methoxy, ethoxy, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, tetrad ecanoyl, pentadecanoyl, hexadecanoyl or heptadecanoyl, heptadecanoyl or heptadecanoyl.
- R1, R2 and R3 can also be acyl radicals.
- R1, R2 and R3 can preferably be acyl radicals having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms and for example formyl, acetyl, propionyl, butyryl, trifluoroacetyl or benzoyl or naphthoyl.
- R1, R2 and R3 can furthermore be amino, methylamino, dimethylamino, methylthio, methylsulfinyl, methylsulfonyl or phenylsulfonyl groups.
- One, two or three methylene groups in the radicals R1, R2 and R3 in alkyl, alkylene, cycloalkyl, cycloalkylene, alkanoyl and cycloalkanoyl can also be replaced by N, O and / or S.
- a hydrocarbon group in R1, R2 and R3 can therefore be any hydrocarbon group in R1, R2 and R3.
- R3 ' is a cyclic hydrocarbon which has a stabilizing effect on the compounds of the general formulas (I) and (II) in comparison with the prior art.
- H atoms in R3 ' can be replaced by functional groups Z.
- R3 ' is preferably a cyclic aliphatic hydrocarbon radical A, as described above, an aromatic hydrocarbon Ar from the groups listed above or a heterocyclic substituent Het as defined above.
- R3 ' is very preferably a cyclic aliphatic or aromatic hydrocarbon radical having 6 to 18 carbon atoms. From this group of compounds the residues mesityl,
- Triisopropylphenyl or cyclohexyl as particularly suitable and led to particularly advantageous properties of the compounds prepared.
- N, P, O or S atoms carry and can include radicals with the meanings OA, NHA, NAA ', PAA', CN, NO 2 , SA, SOA, SO 2 A or SO 2 Ar, where A "A 'and A” can independently of one another take the meanings of A according to the definition given. They can be groups which contain one or more alcohol (OA), aldehyde, carboxylic acid, amine, Have amide, imide, phosphine, ether or thioether functions.
- a group Z preferably has the meaning OA, NHA, NAA 'and PAA'.
- R4 can therefore also be, for example, SO 3 H, F, Cl, a hydroxyl, alkanoyl or cycloalkanoyl radical. You can use methoxy, ethoxy, propionyl, butyryl,
- R4 can also be an acyl radical.
- R4 can preferably be acyl radical having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms and e.g. Formyl, acetyl, propionyl, butyryl, trifluoroacetyl or benzoyl or naphthoyl mean.
- R1, R2 and R4 can furthermore be amino, methylamino, dimethylamino, methylthio, methylsulfinyl, methylsulfonyl or phenylsulfonyl groups.
- One, two or three methylene groups in the radicals R3 'and R4 in alkyl, alkylene, cycloalkyl, cycloalkylene, alkanoyl and cycloalkanoyl can each be replaced by N, O and / or S.
- a hydrocarbon group in R4 can therefore assume the meanings of A, Ar or AAr and an alkyl, alkenyl, aryl, alkylaryl or alkynyl group as defined above, in which one or more H atoms are represented by the above-mentioned functional groups Z can be replaced.
- R4 can be H or have all the meanings of shark, A, Ar and AAr, as indicated above, where in A and Ar H atoms can be replaced by functional groups Z and Shark can mean F, Cl, Br or I.
- Hai preferably denotes Cl or Br.
- R4 independently of one another denotes H, Cl, Br, straight-chain, branched, saturated, mono- or polyunsaturated CrC 7 -alkyl radical, it being possible for one or more H in the alkyl radical to be replaced by Z. ,
- R5 can independently of one another be A, Ar or AAr, as defined above, and in particular can be an alkyl, cycloalkyl or aryl group having up to 10 C atoms.
- R5 is preferably a C 1 -C 6 -alkyl, a C 5 -C 8 -
- Cycloalkyl or a C6-C10 aryl can preferably have the meanings Methyl, ethyl, propyl, i-propyl, butyl, i-butyl, sec-butyl, tert-butyl, pentyl, 1-, 2- or 3-methylbutyl (-C5H1 0 -), 1, 1-, 1, 2- or 2,2-dimethylpropyl (- C 5 H10-), 1-ethylpropyl (-C 5 H 10 -), hexyl (-C 6 H 12 -), 1-, 2-, 3- or 4-methyl pentyl (-C 6 H 12 -), 1, 1-, 1,2-, 1, 3-, 2,2-, 2,3- or 3,3-dimethylbutyl (-C 6 H 12 -), 1 - or 2-ethylbutyl (-C 6 H 12 -),
- Naphthyl, R5 is very preferably cyclohexyl, cyclopentyl, isopropyl and phenyl.
- R6 and R7 can independently be H, A or Ar, it being possible for H atoms in A or Ar to be substituted by alkenyl or alkynyl radicals, with not more than 30 C atoms.
- R6 and R7 can therefore independently of one another be H, alkyl, cycloalkyl, aryl, alkenyl or alkynyl having up to 30 C atoms.
- R6 and R6 is H, CrCio-alkyl, C 6 are preferably - C-io-aryl, C 2 -C ⁇ o alkenyl and C 2 -C 8 alkynyl.
- R6 and R6 can therefore preferably have the meanings methyl, ethyl, propyl, i-propyl, butyl, i-butyl, sec-butyl, tert-butyl, pentyl, 1-, 2- or 3-methylbutyl (-C 5 H 10 -), 1, 1-, 1, 2- or 2,2-dimethylpropyl (-C 5 H 10 -), 1-ethylpropyl (-C 5 H 10 -), hexyl (-C 6 H 12 -), 1 -, 2-, 3- or 4-methylpentyl (-C 6 H ⁇ 2 -), 1, 1-, 1, 2-, 1, 3-, 2,2-, 2,3- or 3,3-dimethylbutyl (-C 6 H 12 -), 1- or 2-ethylbutyl (-C 6 H ⁇ 2 -), 1-ethyl-1-methylpropyl (-C 6 H ⁇ 2 -), 1-ethyl-2-methylpropyl (-C 6 H ⁇ 2 -
- X is a monovalent anion that serves to balance the charge. It is in the compounds of general formulas (V) and (VI) or (Va) and (Vla) is bound as a ligand to a double positively charged ruthenium central atom. Depending on the electronegativity of the anion X, this bond can be a coordinative bond which is formed by free electron pairs of the anion or an ionic bond.
- the anions X contained in the compounds (I) and (II) or (V) and (VI) can independently of one another be halide (Hai) from the group Br “ , Cl “ , J “ and F “ , pseudohalide such as cyanide (CN “ ) and thiocyanate (SCN “ ), alkoxide, aryl oxide, alkyl, aryl, carboxyl, etc.
- X is preferably halide, very preferably Cl or Br.
- the compounds of the general formulas (I) and (II) substituted by silyl groups on the second nitrogen atom of the imidazole ring can be prepared in a simple manner by reacting R3-substituted imidazole or substituted 4,5-dihydroimidazole with chlorine, bromine or Iodine-containing alkoxysilanes Hal-R-SiR ' n (OR') 3 -n take place without the addition of another solvent in a protective gas atmosphere. However, it is also possible to carry out the reaction in an inert aprotic organic solvent.
- the reaction takes place within a short time while maintaining the reaction temperature or requires several days.
- the reaction temperature is in a range from 20 to + 200 ° C, preferably from 20 to 100 ° C and very preferably between 60 and 100 ° C.
- the products (I) and (II) formed can be isolated in pure form as stable substances by known methods and processed further according to Method A to give the compounds of the general formulas (V) and (VI) or immobilized on a support.
- the compounds of the general formulas (III) and (IV) are prepared by reacting the alkoxysilyl-functionalized imidazolium salts (I) or alkoxysilyl-functionalized 4,5-dihydroimidazolium salts (II) with a suitable base in anhydrous, inert, aprotic organic solvents in a protective gas atmosphere.
- This reaction can optionally be carried out directly after the preparation of the imidazolium salts (I) or 4,5-dihydroimidazolium salts (II) without prior purification.
- Bases suitable for this reaction are metal alcoholates of the general formula MOR or bases selected from the group of metal hydrides, MH, metal amides, MNH 2 and ammonia in an anhydrous, inert, aprotic organic solvent. NH 3 / NaH, a metal hydride or a is preferred
- the starting compounds of the general formulas (I) and (II) can in a suitable solvent, such as. B. be pre-dissolved or suspended in an ether. Nitrogen or argon can serve as the protective gas atmosphere. This reaction can take place in a temperature range from -78 ° C to + 100 ° C, preferably from -40 ° C to +60 ° C during a reaction time of 1 minute to 6 hours.
- the products of the general formulas (III) or (IV) formed can, if appropriate after isolation of solid by-products and removal of the volatile constituents, be isolated in a simple manner by extraction and crystallization, or directly by method B to give the compounds of the general formulas (V) or (VI) are reacted or immobilized on an inorganic oxide as a carrier.
- Inorganic oxides which contain active OH groups on the surface and are thus capable of reacting with the starting compounds (I) to (VI) can be used as carriers.
- Natural or chemically produced particulate or monolithic oxides of silicon, boron, aluminum, titanium and zirconium or else oxide mixtures can be used as inorganic oxides.
- Particulate or monolithic oxides of silicon or aluminum or their mixed oxides and zeolites are preferably used.
- Particulate or monolithic oxides of silicon are particularly preferably used.
- the silicon-containing materials can be a silica gel or naturally occurring silicate, which are derived from chain, band and layered silicas.
- the advantages of the compounds of the general formulas (Ia) and (Ila) compared to the prior art are that the sterically demanding radical R3 'makes them very stable and therefore they are suitable precursors for the synthesis of the thermally very sensitive N-heterocyclic carbenes Ligands and the metal complexes that can be synthesized therefrom.
- the advantages of the compounds of the general formulas (purple) and (IVa) compared to the prior art are that they are accessible for the first time and that they are also thermally much more stable than their unsupported analogues.
- the weakly bound phosphine ligand dissociates from the catalytically active ruthenium center into the solution, so that the catalytically active species remains bound to the support during the entire catalysis and thus no catalyst loss through leaching occurs.
- the compounds of the general formulas (Ia) to (Via) are very simple and can be obtained in quantitative yields.
- inorganic carriers that consist either of particles or of a monolith. Consequently, all application reactions can be carried out in batch processes as well as in continuous processes.
- the compounds of the general formulas (Ia) and (Ila) can be used as immobilized reaction media, immobilized ionic ones
- the compounds of the general formulas (purple) and (IVa) can be used as starting materials for the preparation of immobilized N-heterocyclic carbene-metal complexes and as immobilized ligands in catalytic reactions, especially in ruthenium-catalyzed metathesis reactions, palladium-catalyzed Heck or Suzuki reactions, rhodium-catalyzed hydrogenations, furan syntheses, hydroformulation, isomerizations or hydrosilylation.
- the compounds of the general formulas (Va) and (Via) can be used as immobilized
- Catalysts in organic and organometallic synthesis can be used as catalysts in C-C coupling reactions, hydrogenations, isomerizations, silylations and hydroformylations.
- the new compounds are particularly suitable as immobilized catalysts for C-C coupling reactions like that
- CM cross metathesis
- RCM ring closure metathesis
- ROMP ring opening metathesis polymerization
- ADMET acyclic diene metathesis polymerization
- the monolith predried overnight in a drying cabinet at 80 ° C., is installed in the furnace of the flow-through apparatus, which is heated to 30 ° C. It is rinsed for 1 h with CH 2 CI 2 at a flow of 0.05 ml / min.
- 1.03 g (2.00 mmol) of 1-mesityl-3- [3- (triethoxysilyl) propyl] imidazolium chloride dissolved in 50 ml of CH 2 Cl 2 are added to the sample loop in 10 ml portions and passed through at a flow of 0.3 ml / min pumped the monolith. It was washed with CH 2 Cl 2 overnight with a flow of 0.1 ml / min.
- Silica gel 60 is separated from the solution by filtration and repeated washing with heptane and tetrahydrofuran. The functionalized
- Silica gel is dried in a high vacuum.
- the SiO 2 monolith is dried overnight in a drying cabinet at 120 ° C and then connected to the flow circulator's thermostats.
- the chromolite is rinsed for 1 h with CH 2 CI 2 at a flow of 0.5 ml / min. 950 mg ⁇ 1-mesityl-3- [3-
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- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
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Priority Applications (3)
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EP04763282A EP1654064A2 (de) | 2003-08-11 | 2004-07-16 | Immobilisierte immidazole und ruthenium-katalysatoren |
JP2006522921A JP2007501695A (ja) | 2003-08-11 | 2004-07-16 | 固定化イミダゾールおよびルテニウム触媒 |
US10/567,742 US20060293526A1 (en) | 2003-08-11 | 2004-07-16 | Immobilised imidazoles and ruthenium catalysts |
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DE10337118 | 2003-08-11 | ||
DE10337118.4 | 2003-08-11 |
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WO2005016524A3 WO2005016524A3 (de) | 2005-05-12 |
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US (1) | US20060293526A1 (de) |
EP (1) | EP1654064A2 (de) |
JP (1) | JP2007501695A (de) |
CN (1) | CN1835801A (de) |
TW (1) | TW200523027A (de) |
WO (1) | WO2005016524A2 (de) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102004060247A1 (de) * | 2004-12-15 | 2006-06-29 | Studiengesellschaft Kohle Mbh | Neue N-heterocyclische Carbene und ihre Anwendung in der Katalyse |
EP2082804A1 (de) * | 2008-01-25 | 2009-07-29 | CPE Lyon Formation Continue et Recherche | Hybride organisch-anorganische Materialien mit stabilisiertem Carben |
CN104030973A (zh) * | 2014-06-13 | 2014-09-10 | 上海应用技术学院 | 一种1,4-二氢吡啶类化合物的制备方法 |
US9427731B2 (en) | 2009-12-03 | 2016-08-30 | Materia, Inc. | Supported olefin metathesis catalysts |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
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DE19815275B4 (de) * | 1998-04-06 | 2009-06-25 | Evonik Degussa Gmbh | Alkylidenkomplexe des Rutheniums mit N-heterozyklischen Carbenliganden und deren Verwendung als hochaktive, selektive Katalysatoren für die Olefin-Metathese |
AU2007263808B2 (en) * | 2006-06-30 | 2012-04-19 | F. Hoffmann-La Roche Ag | New ruthenium complexes as catalysts for metathesis reactions |
WO2008132962A1 (ja) * | 2007-04-20 | 2008-11-06 | Niigata University | オレフィンメタセシス触媒及びそれを用いたメタセシス反応によるオレフィン反応生成物の製造方法 |
EP2632929A4 (de) * | 2010-10-28 | 2014-03-26 | Basf Se | N-heterozyklische carbenkomplexe sowie ihre herstellung und verwendung |
US20120289617A1 (en) * | 2011-05-10 | 2012-11-15 | Saudi Arabian Oil Company | Hybrid Catalyst for Olefin Metathesis |
EP2744816B1 (de) * | 2011-08-15 | 2017-10-11 | The Governing Council Of The University Of Toronto | Rutheniumbasierte komplexe katalysatoren |
US9890239B2 (en) | 2013-09-04 | 2018-02-13 | California Institute Of Technology | Functionalized linear and cyclic polyolefins |
CN108043442B (zh) * | 2017-12-07 | 2021-03-19 | 苏州大学 | 碳负载的钌纳米材料及其制备方法与在催化醇与芳香二胺反应中的应用 |
US11998900B2 (en) * | 2022-07-13 | 2024-06-04 | Baker Hughes Oilfield Operations Llc | Immobilizing metal catalysts in a porous support via additive manufacturing and chemical vapor transformation |
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- 2004-07-16 EP EP04763282A patent/EP1654064A2/de not_active Withdrawn
- 2004-07-16 US US10/567,742 patent/US20060293526A1/en not_active Abandoned
- 2004-07-16 JP JP2006522921A patent/JP2007501695A/ja active Pending
- 2004-07-16 WO PCT/EP2004/007939 patent/WO2005016524A2/de not_active Application Discontinuation
- 2004-07-16 CN CN200480022981.4A patent/CN1835801A/zh active Pending
- 2004-08-10 TW TW093123927A patent/TW200523027A/zh unknown
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DE19954485A1 (de) * | 1999-11-12 | 2001-05-17 | Inst Brennstoffchemie Und Phys | Neuartige immobilisierte Ionic Liquids, ihre Darstellung und Verwendung |
US20020198100A1 (en) * | 2001-05-30 | 2002-12-26 | Mehnert Christian Peter | Ionic liquid compositions |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102004060247A1 (de) * | 2004-12-15 | 2006-06-29 | Studiengesellschaft Kohle Mbh | Neue N-heterocyclische Carbene und ihre Anwendung in der Katalyse |
EP2082804A1 (de) * | 2008-01-25 | 2009-07-29 | CPE Lyon Formation Continue et Recherche | Hybride organisch-anorganische Materialien mit stabilisiertem Carben |
WO2009092814A1 (en) * | 2008-01-25 | 2009-07-30 | Cpe Lyon Formation Continue Et Recherche | Hybrid organic-inorganic materials that contain stabilized carbene |
US8871877B2 (en) | 2008-01-25 | 2014-10-28 | Universite Claude Bernard Lyon 1 (Ucbl) | Hybrid organic-inorganic materials that contain stabilized carbene |
US9427731B2 (en) | 2009-12-03 | 2016-08-30 | Materia, Inc. | Supported olefin metathesis catalysts |
CN104030973A (zh) * | 2014-06-13 | 2014-09-10 | 上海应用技术学院 | 一种1,4-二氢吡啶类化合物的制备方法 |
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US20060293526A1 (en) | 2006-12-28 |
TW200523027A (en) | 2005-07-16 |
CN1835801A (zh) | 2006-09-20 |
EP1654064A2 (de) | 2006-05-10 |
JP2007501695A (ja) | 2007-02-01 |
WO2005016524A3 (de) | 2005-05-12 |
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