DE3101380A1 - Organometal complex compounds, their preparation and their use - Google Patents
Organometal complex compounds, their preparation and their useInfo
- Publication number
- DE3101380A1 DE3101380A1 DE19813101380 DE3101380A DE3101380A1 DE 3101380 A1 DE3101380 A1 DE 3101380A1 DE 19813101380 DE19813101380 DE 19813101380 DE 3101380 A DE3101380 A DE 3101380A DE 3101380 A1 DE3101380 A1 DE 3101380A1
- Authority
- DE
- Germany
- Prior art keywords
- group
- general formula
- complex compounds
- compound
- denotes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 8
- 239000010948 rhodium Substances 0.000 claims abstract description 8
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000460 chlorine Substances 0.000 claims abstract description 5
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 239000010703 silicon Substances 0.000 claims abstract description 4
- 229910052718 tin Chemical group 0.000 claims abstract description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 3
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 3
- 239000011669 selenium Substances 0.000 claims abstract description 3
- 125000005369 trialkoxysilyl group Chemical group 0.000 claims abstract description 3
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims abstract 2
- 239000003054 catalyst Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 125000002524 organometallic group Chemical group 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- KGFYHTZWPPHNLQ-AWEZNQCLSA-N rivaroxaban Chemical group S1C(Cl)=CC=C1C(=O)NC[C@@H]1OC(=O)N(C=2C=CC(=CC=2)N2C(COCC2)=O)C1 KGFYHTZWPPHNLQ-AWEZNQCLSA-N 0.000 claims description 2
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 claims 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 abstract description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract description 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 abstract 1
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 abstract 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 1
- 125000004890 (C1-C6) alkylamino group Chemical group 0.000 abstract 1
- 239000005864 Sulphur Substances 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000969 carrier Substances 0.000 description 8
- VSMOENVRRABVKN-UHFFFAOYSA-N oct-1-en-3-ol Chemical compound CCCCCC(O)C=C VSMOENVRRABVKN-UHFFFAOYSA-N 0.000 description 6
- -1 platinum group metals Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000004927 clay Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007172 homogeneous catalysis Methods 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- SPTZBOGAKAEUIE-UHFFFAOYSA-N trimethoxy(2-trimethylsilylsulfanylethyl)silane Chemical compound CO[Si](OC)(OC)CCS[Si](C)(C)C SPTZBOGAKAEUIE-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- NMRPBPVERJPACX-UHFFFAOYSA-N octan-3-ol Chemical compound CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000010414 supernatant solution Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- WPWHSFAFEBZWBB-UHFFFAOYSA-N 1-butyl radical Chemical group [CH2]CCC WPWHSFAFEBZWBB-UHFFFAOYSA-N 0.000 description 1
- GJWHXWMUGWZNTO-UHFFFAOYSA-N 2,2-dimethylpropane Chemical group [CH2]C(C)(C)C GJWHXWMUGWZNTO-UHFFFAOYSA-N 0.000 description 1
- DVNPFNZTPMWRAX-UHFFFAOYSA-N 2-triethoxysilylethanethiol Chemical compound CCO[Si](CCS)(OCC)OCC DVNPFNZTPMWRAX-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 101150027068 DEGS1 gene Proteins 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- VEQOALNAAJBPNY-UHFFFAOYSA-N antipyrine Chemical compound CN1C(C)=CC(=O)N1C1=CC=CC=C1 VEQOALNAAJBPNY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000006324 decarbonylation Effects 0.000 description 1
- 238000006606 decarbonylation reaction Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001030 gas--liquid chromatography Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- HCBPHBQMSDVIPZ-UHFFFAOYSA-N methylcyclohexatriene Chemical group CC1=CC=C=C[CH]1 HCBPHBQMSDVIPZ-UHFFFAOYSA-N 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 229910003452 thorium oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical group CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0073—Rhodium compounds
- C07F15/008—Rhodium 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
- B01J31/1616—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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/226—Sulfur, e.g. thiocarbamates
-
- 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
-
- 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
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/512—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being a free hydroxyl group
-
- 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
- B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
- B01J2231/52—Isomerisation reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/827—Iridium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
Description
Metallorganische Komplexverbindungen, Organometallic complex compounds,
Verfahren zu deren Herstellung und deren Verwendung deren Verwendung Die Erfindung betrifft metallorganische Komplexverbindungen der Platingruppenmetalle Rhodium und/oder Iridium, die als Kohlenwasserstoffumwandlungskatalysatoren verwendet werden können. Process for their production and their use, their use The invention relates to organometallic complex compounds of the platinum group metals Rhodium and / or iridium used as hydrocarbon conversion catalysts can be.
Aus Angewandte Chemie", 1980, Heft 1, Seiten 60 bis 61, ist u-Alkylthio- und /u-Arylthio-/u-chloro-dicarbonyl-bis-(tritert-butylphosphan)-dirhodium der allgemeinen Formel bekannt, worin (t-Bu) eine Tertiärbutylgruppe bedeutet und R eine Isopropyl-, Normalbutyl- oder Tertiärbutylgruppe oder einen Phenylrest, p-Tolylrest oder p-Chlorphenylrest bedeutet. Aus der genannten Veröffentlichung ist es auch bereits bekannt, derartige metallorganische Komplexverbindungen als Hydrierungs-, Decarbonylierungs- und Isomerisierungskatalysatoren zu verwenden. Diese Verbindungen können aber nur für homogene Katalysen verwendet werden.From Angewandte Chemie ", 1980, No. 1, pages 60 to 61, u-alkylthio- and / u-arylthio- / u-chloro-dicarbonyl-bis- (tritert-butylphosphine) -dirhodium of the general formula known, in which (t-Bu) denotes a tertiary butyl group and R denotes an isopropyl, normal butyl or tertiary butyl group or a phenyl radical, p-tolyl radical or p-chlorophenyl radical. It is also already known from the publication mentioned that such organometallic complex compounds can be used as hydrogenation, decarbonylation and isomerization catalysts. However, these compounds can only be used for homogeneous catalysis.
Aus "Tetrahedron Letters", Band 21, (1980), Seiten 459 bis 462, ist es weiterhin bekannt, einen an Styrol trägerfixierten Rhodiumkomplex der Formel herzustellen und als Katalysator für die Hydrierung von Cyclohexan zu verwenden. Ein solcher trägergebundener Rhodiumkomplex besitzt aber relativ geringe katalytische Aktivität und kann infolge seiner Bindung an einen organischen Träger nur in beschränktem Umfang für Kohlenwasserstoffumwandlungsverfahren eingesetzt werden.From "Tetrahedron Letters", Volume 21, (1980), pages 459 to 462, it is also known to have a rhodium complex of the formula supported on styrene and to use as a catalyst for the hydrogenation of cyclohexane. Such a carrier-bound rhodium complex, however, has relatively low catalytic activity and, as a result of its binding to an organic carrier, can only be used to a limited extent for hydrocarbon conversion processes.
Die der Erfindung zugrundeliegende Aufgabe bestand nun darin, Rhodium- und/oder Iridiumkomplexverbindungen der eingangs genannten Art mit erhöhter katalytischer Aktivität zu bekommen.The object underlying the invention was now to rhodium and / or iridium complex compounds of the type mentioned with increased catalytic Get activity.
Insbesondere war es Ziel der Erfindung, solche katalytisch hoch aktiven metallorganischen Komplexverbindungen zu bekommen, die sich auf einem Träger, insbesondere einem anorganischen Träger fest binden und in dieser Form als Hybridkatalysatoren verwenden lassen.In particular, it was the aim of the invention to find such catalytically highly active to get organometallic complex compounds, which are on a support, in particular firmly bind an inorganic carrier and in this form as hybrid catalysts let use.
Die erfindungsgemäßen metallorganischen Komplexverbindungen besitzen die allgemeine Formel I worin A Rhodium oder Iridium, Y Phosphor, Arsen oder Antimon, X Chlor oder Brom, Q Schwefel oder Selen, R eine verzweigte Alkylgruppe mit wenigstens 4 C-Atomen, eine C7-18-Cycloalkylgruppe, einen gegebenenfalls durch ein bis fünf Halogenatome, C1-16-Alkyil-, -Alkoxy-oder -Alkylaminogruppen, CF3-Reste oder OH-Gruppen substituierten Phenyl-IV rest oder einen Rest der allgemeinen Formel -CH2-M-(R ) 3 oder -CHtM(RIV)3 72 worin M Silicium, Germanium oder Zinn und RIV eine C1 4-Alkylgruppe ist, und R' eine Trialkoxysilylgruppe der allgemeinen Formel (R"O) 3Si-R' -worin R" eine C112-Alkyl- oder Phenylgruppe und R''' die Gruppe -(-CH2-)-n oder -[(CH2)nZ]-m -(-CH2)n bedeutet, in denen n 2 bis 6 und m 1 bis 6 und Z -O-, -S-, -NH-, -P-Phenyl-, -CO-NH-, -COO-, P-Phenylen, oder die Gruppe (L = -O-, -S- oder -CH2) ist, bedeutet.The organometallic complex compounds according to the invention have the general formula I. where A rhodium or iridium, Y phosphorus, arsenic or antimony, X chlorine or bromine, Q sulfur or selenium, R a branched alkyl group with at least 4 carbon atoms, a C7-18 cycloalkyl group, one optionally with one to five halogen atoms, C1 -16-alkyl, -alkoxy or -alkylamino groups, CF3 radicals or OH groups substituted phenyl-IV radical or a radical of the general formula -CH2-M- (R) 3 or -CHtM (RIV) 3 72 in which M Silicon, germanium or tin and RIV is a C1 4 -alkyl group, and R 'is a trialkoxysilyl group of the general formula (R "O) 3Si-R' - where R" is a C112-alkyl or phenyl group and R '''is the group - (-CH2 -) - n or - [(CH2) nZ] -m - (- CH2) n, in which n is 2 to 6 and m is 1 to 6 and Z is -O-, -S-, -NH-, -P-phenyl-, -CO-NH-, -COO-, P-phenylene, or the group (L = -O-, -S- or -CH2) means.
Diese Verbindungen besitzen überraschenderweise bei Verwendung in einer homogenen Katalyse in Kohlenwasserstoffumwandlungsverfahren eine wesentlich bessere katalytische Aktivität als die strukturell am nächsten liegenden Verbindungen, die aus "Angewandte Chemie", 1980, Seite 60, bekannt sind. Außerdem lassen sich die erfindungsgemäßen Komplexverbindungen an anorganische Träger großer Oberfläche mit Hydroxylgruppen, wie an Ton, Glas, Metalloxide, Silikate oder Zeolithe, binden. Sie besitzen an diesen Trägern eine hohe Bindungsfestigkeit und gleichzeitig eine hohe katalytische Aktivität, die derjenigen strukturell ähnlicher Verbindungen, die jedoch nur in homogener Katalyse verwendbar sind, zumindest gleichwertig ist.These compounds surprisingly have when used in homogeneous catalysis in hydrocarbon conversion processes is essential better catalytic activity than the structurally closest compounds, from "Angewandte Chemie", 1980, page 60, are known. In addition, you can the complex compounds according to the invention on inorganic carriers with a large surface with hydroxyl groups, such as on clay, glass, Metal oxides, silicates or Zeolites, bind. You have a high bond strength on these carriers and at the same time a high catalytic activity, which is structurally more similar to that Compounds that can only be used in homogeneous catalysis, at least equivalent is.
Bevorzugt sind solche metallorganischen Komplexverbindungen nach der Erfindung, in denen A Rhodium bedeutet, in denen Y Phosphor oder Arsen, besonders Phosphor bedeutet, in denen X Chlor bedeutet und in denen Q Schwefel bedeutet.Such organometallic complex compounds are preferred according to the Invention in which A is rhodium, in which Y is phosphorus or arsenic, especially Phosphorus means in which X means chlorine and in which Q means sulfur.
Weiterhin sind bevorzugt jene Komplexverbindungen, in denen R eine verzweigte Alkylgruppe mit 4 bis 12, vorzugsweise 4 bis 8 Kohlenstoffatomen, einen Phenylrest, einen mit jeweils einem der oben angegebenen Substituenten substituierten Phenylrest oder eine der Gruppen -CH2-M-(CH3)3 oder-CHzM(CH3)3-72, worin M Silicium, Germanium oder Zinn ist, bedeutet. Spezielle Substituenten R sind beispielsweise der Tertiärbutylrest, Neopentylrest, Adamantylrest oder Norbornylrest. Die Tertiärbutylgruppe ist besonders bevorzugt. Allgemein läßt sich für R sagen, daß diese Gruppe eine sterisch sperrige Gruppe sein muß, so daß n-Alkylgruppen nicht in Betracht kommen.Also preferred are those complex compounds in which R is branched alkyl group having 4 to 12, preferably 4 to 8 carbon atoms Phenyl radical, one substituted by one of the substituents indicated above Phenyl radical or one of the groups -CH2-M- (CH3) 3 or -CHzM (CH3) 3-72, in which M is silicon, Is germanium or tin, means. Special substituents R are for example the tertiary butyl radical, neopentyl radical, adamantyl radical or norbornyl radical. The tertiary butyl group is particularly preferred. In general it can be said for R that this group is a must be sterically bulky group, so that n-alkyl groups are out of the question.
Bevorzugte Gruppen R' sind solche der oben angegebenen Formel, worin R" eine Methyl- oder Äthylgruppe, besonders eine Methylgruppe ist und worin R' " die Gruppe -(CH2)-2 4 oder -(CH2)p-Z-(CH2)p- bedeutet, worin Z -O-, -NH- oder -CO-NH- und p 2 bis 4 ist.Preferred groups R 'are those of the formula given above, in which R "is a methyl or ethyl group, especially a methyl group and in which R '" the group - (CH2) -2 4 or - (CH2) p-Z- (CH2) p- denotes, in which Z -O-, -NH- or -CO-NH- and p is 2-4.
Soweit R ein durch Alkyl-, Alkoxy- oder Alkylaminogruppen substituierter Phenylrest ist, ist es bevorzugt, daß dieser jeweils 1 bis 4 Kohlenstoffatome enthält.If R is substituted by alkyl, alkoxy or alkylamino groups Is phenyl, it is preferred that this contains 1 to 4 carbon atoms in each case.
Die metallorganischen Komplexverbindungen nach der Erfindung werden zweckmäßig in der Weise hergestellt, daß man eine Verbindung der allgemeinen Formel II worin A, Y, X und R die obige Bedeutung haben, mit einer Verbindung der allgemeinen Formel R'QSi (CH3)3 worin R' und Q die obige Bedeutung haben, unter Bildung einer Verbindung der obigen Formel I sowie von (CH3)3SiX umsetzt.The organometallic complex compounds according to the invention are advantageously prepared in such a way that a compound of the general formula II wherein A, Y, X and R have the above meaning, with a compound of the general formula R'QSi (CH3) 3 wherein R 'and Q have the above meaning, to form a compound of the above formula I and of (CH3) 3SiX implements.
Die Verbindung II erhält man zweckmäßig durch Umsetzung der bekannten Verbindung der allgemeinen Formel III worin A und X wie oben definiert sind, wobei X vorzugsweise Cl bedeutet, mit einer Verbindung der allgemeinen Formel R3Y.The compound II is expediently obtained by reacting the known compound of the general formula III wherein A and X are as defined above, where X is preferably Cl, with a compound of the general formula R3Y.
Die Verbindung II braucht nicht isoliert zu werden, sondern dem diese Verbindung enthaltenden Reaktionsgemisch kann die Verbindung R'QSi(CH3)3 direkt zugesetzt werden. Sowohl die Bildung der Verbindung II als auch die weitere Umsetzung zur Verbindung I kann bei Umgebungstemperatur erfolgen, wobei bei entsprechender Auswahl des Lösungsmittels die Verbindung I aus dem Reaktionsmedium ausfällt und so leicht von unumgesetzten Ausgangsverbindungen und (CH3)3SiCl abgetrennt werden kann.Compound II does not need to be isolated, but rather this one Compound-containing reaction mixture can direct the compound R'QSi (CH3) 3 can be added. Both the formation of the compound II and the further implementation to compound I can be carried out at ambient temperature, with the appropriate Selection of the solvent the compound I precipitates from the reaction medium and so easily separated from unreacted starting compounds and (CH3) 3SiCl can.
Beispielsweise arbeitet man in dem Lösungsmittel Pentan, in dem zunächst die Verbindung III gelöst und sodann mit der Verbindung R3Y versetzt wird. Die CO-Entwicklung zeigt die Umsetzung an.For example, one works in the solvent pentane, in which initially the compound III is dissolved and then mixed with the compound R3Y. The CO development shows the implementation.
Nach dem Aufhören der CO-Entwicklung hat sich gewöhnlich eine klare Lösung gebildet, die die Verbindung II enthält. Durch Zngsame Zugabe der Verbindung R'QSi(CH3)3 bildet sich dann bei Umgebungstemperatur die Verbindung I, die entweder als Niederschlag ausfällt und in dieser Form in üblicher Weise abgetrennt werden kann, oder, wenn sie in Lösung bleibt, im Vakuum von Lösungsmittel befreit werden kann.After the CO evolution has stopped, there is usually a clear one Formed solution which contains the compound II. By slowly adding the compound R'QSi (CH3) 3 then forms the compound I at ambient temperature, which either precipitates out as a precipitate and is separated off in this form in the customary manner can, or, if it remains in solution, be freed from solvent in vacuo can.
Die erfindungsgemäßen Verbindungen können sowohl an organische als auch an anorganische Träger mit Hydroxylgruppen fixiert werden, wobei bevorzugt die Fixierung auf anorganischen Trägern erfolgt, da diese in Kohlenwasserstoffumwandlungsverfahren einen breiteren Anwendungsbereich haben und höhere Lebensdauer besitzen.The compounds according to the invention can be applied to both organic and can also be fixed to inorganic supports with hydroxyl groups, being preferred the fixation takes place on inorganic supports, as these take place in hydrocarbon conversion processes have a wider range of applications and have a longer service life.
Geeignete anorganische Träger sind alle jene, die eine große Oberfläche besitzen und auf der Oberfläche Hydroxylgruppen gebunden haben. Beispiele hierfür sind feuerfeste anorqanische Oxidträger aus einem in der Natur vorkommenden Material, wie Ton und Silikaten, z. B. Fullererde, Atapulguston, Feldspat, Haloysit, Montmorillonit, Kaolin oder Diatomeenerde, wobei diese anorganischen Oxidträger durch Trocknen, Caicinieren,Dämpfen oder Säurebehandlung aktiviert sein können. Andere geeignete Träger sind künstlich hergestellte feuerfeste anorganische Oxide, wie Tonerde, Kieselsäure, Zirkonoxid, Boroxid, Thoriumoxid, Magnesiumoxid, Titanoxid oder Chromoxid. Bevorzugte anorganische Träger sind Tonerde- und Kieselsäureträger. Andere geeignete anorganische Träger sind Glas, Silikate oder Zeolithe.Suitable inorganic supports are all those that have a large surface area own and bonded to the surface hydroxyl groups to have. Examples of this are refractory inorganic oxide carriers from one in nature occurring material such as clay and silicates, e.g. B. Fuller's earth, atapulgous clay, feldspar, Haloysite, montmorillonite, kaolin or diatomaceous earth, these being inorganic oxide carriers activated by drying, caicinating, steaming or acid treatment. Other suitable carriers are man-made refractory inorganic oxides, such as alumina, silica, zirconium oxide, boron oxide, thorium oxide, magnesium oxide, titanium oxide or chromium oxide. Preferred inorganic carriers are alumina and silica carriers. Other suitable inorganic carriers are glass, silicates or zeolites.
Der Träger kann eine in der Kohlenwasserstoffumwandlungstechnik übliche Form haben, wie die von Kugeln, Granalien, Ringen oder Körnern, wobei die Kugelform aus Gründen der Packung der Katalysatorschicht und Stabilitäts- und damit Lebesdauergründen bevorzugt ist.The carrier can be one conventional in the hydrocarbon conversion art Shape like that of balls, granules, rings or grains, being the spherical shape for reasons of the packing of the catalyst layer and reasons of stability and thus lifespan is preferred.
Die Bindung der erfindungsgemäßen Komplexverbindungen an den Träger erfolgt über die Gruppen R", die mit den Hydroxylgruppen des Trägers unter Abspaltung von R"OH in Reaktion treten und dabei die katalytischen Komplexverbindungen durch kovalente Bindungen an den Träger binden. Für die Verwendung eines Kieselsäureträgers, wie beispielsweise von aktiviertem Kieselgel, wird durch die nachfolgende Gleichung die Bindung an den Träger Beispiel halber für spezielle Verbindungen nach der Erfindung dargestellt. The complex compounds according to the invention are bonded to the carrier via the groups R ″, which react with the hydroxyl groups of the carrier with elimination of R ″ OH and thereby bind the catalytic complex compounds to the carrier by covalent bonds. For the use of a silica support, such as activated silica gel, the following equation shows the bond to the support for the sake of example for specific compounds according to the invention.
Die Fixierung der erfindungsgemäßen Verbindungen auf einem organischen oder speziell anorganischen Trägermaterial erfolgt gewöhnlich bei Raumtemperatur durch mehrstündiges Rühren, worauf die überstehende Lösung abdekantiert und der Träger beispielsweise mit Pentan gewaschen und sodann im Vakuum getrocknet wird.The fixation of the compounds according to the invention on an organic or especially inorganic support material is usually carried out at room temperature by stirring for several hours, whereupon the supernatant solution is decanted and the Carrier is washed, for example, with pentane and then dried in vacuo.
Durch die folgenden Beispiele wird die Erfindung weiter erläutert.The invention is further illustrated by the following examples.
Beispiel 1 Herstellung von /u-Chloro-/u-2-(trimethyloxysilyl)-äthylsulfidodicarbonyl-bis-tri-(tert.-butyl)-phosphin7-dirhodium 300 mg (0,77 mMol) /u-Dichlorotetracarbonyldirhodium wurden in 10 ml Pentan mit 300 mg (1,48 mMol) Tri-(tert.-butyl)-phosphin versetzt. Unter CO-Entwicklung entstand eine klare Lösung, die noch 5 Stunden bei Raumtemperatur weiter gerührt wurde.Example 1 Preparation of /u-Chloro-/u-2-(trimethyloxysilyl )-ethylsulfidodicarbonyl-bis-tri-(tert.-butyl) -phosphine7-dirhodium 300 mg (0.77 mmol) / u-Dichlorotetracarbonyldirhodium were in 10 ml of pentane with 300 mg (1.48 mmol) of tri- (tert-butyl) phosphine are added. Developed under CO a clear solution, which was stirred for a further 5 hours at room temperature.
Nunmehr wurden zu dem Reaktionsgemisch 0,77 mMol 2-(Trimethoxysilyl)-äthylthiotrimethylsilan langsam zugetropft. Die Reaktionslösung wurde filtriert und im Vakuum eingedampft, wobei die in der Überschrift angegebene Verbindung als orange farbiger Feststoff erhalten wurde.0.77 mmol of 2- (trimethoxysilyl) ethylthiotrimethylsilane were then added to the reaction mixture slowly added dropwise. The reaction solution was filtered and evaporated in vacuo, the compound given in the title as an orange solid was obtained.
Analyse: Für C31H66Cl02SP2Rh2 ber. C 43,92% H 7,97% gef. C 43,25% H 7,98% Das als Ausgangsverbindung verwendete 2-(Trimethoxysilyl)-äthylthiotrimethylsilan wurde wie folgt hergestellt: Zu 20 g (0,09 Mol) 2-(Triäthoxysilyl)-äthylmercaptan wurden 14,3 g (0,044 Mol) wasserfreies Bleiacetat in absolutem Methanol zugetropft. Bedingt durch das Lösungsmittel Methanol wurden bei der Reaktion gleichzeitig die Äthoxygruppen gegen Methoxygruppen ausgetauscht.Analysis: Calculated for C31H66Cl02SP2Rh2. C 43.92% H 7.97% found. C 43.25% H 7.98% The 2- (trimethoxysilyl) ethylthiotrimethylsilane used as the starting compound was prepared as follows: To 20 g (0.09 mol) of 2- (triethoxysilyl) ethyl mercaptan 14.3 g (0.044 mol) of anhydrous lead acetate in absolute methanol were added dropwise. Due to the methanol solvent, the Ethoxy groups exchanged for methoxy groups.
Es bildete sich sofort ein gelber Niederschlag, der nach 12stündigem Rühren abfiltriert, mit Methanol gewaschen und im Vakuum getrocknet wurde.A yellow precipitate formed immediately, which after 12 hours Stirring was filtered off, washed with methanol and dried in vacuo.
0,05 Mol des so erhaltenen Bleimercaptids wurden mit etwa 60 ml Trimethylchlorsilan unter Erhitzen umgesetzt. Das Ende der Reaktion zeigte sich durch den Farbwechsel des Niederschlages von gelb nach weiß. Das gebildete Bleidichlorid wurde abfiltriert und die verbleibende Flüssigkeit fraktioniert destilliert. Das 2-(Trimethoxysilyl)-äthyl-thiotrimethylsilan wurde so in einer Ausbeute von 90% der Theorie als farblose Flüssigkeit mit einem P Ot1Torr = 500C erhalten.0.05 mol of the lead mercaptide thus obtained was mixed with about 60 ml of trimethylchlorosilane implemented under heating. The end of the reaction was indicated by the color change of the precipitation from yellow to white. The lead dichloride formed was filtered off and the remaining liquid is fractionally distilled. 2- (Trimethoxysilyl) -ethyl-thiotrimethylsilane was so in a yield of 90% of theory as a colorless liquid with a Obtained P Ot1Torr = 500C.
Beispiel 2 Fixierung von /u-Chloro-/u-2-(trimethoxysilyl)-äthylsulfidodicarbonyl-bis-tri- (tert.-butyl) -phosphin/-dirhodium an Silicagel Das gemäß Beispiel 1 hergestellteu-Chloro- u-2-(trimethoxysLyl)-äthylsulfido-dicarbonyl-bis-tri-(tert.-butyl)-phosphin7-dirhodium wurde in Pentan gelöst und mit 5 g getrocknetem Silicagel versetzt. 12 Stunden wurde bei Raumtemperatur gerührt und anschließend die überstehende Lösung abdekantiert. Nach dem Waschen mit Pentan wurde das Silicageladsorbat im Vakuum getrocknet.Example 2 fixation of / u-chloro- / u-2- (trimethoxysilyl) -äthylsulfidodicarbonyl-bis-tri- (tert-Butyl) phosphine / dirhodium on silica gel The u-chloro produced according to Example 1 u-2- (trimethoxysLyl) -ethylsulfido-dicarbonyl-bis-tri- (tert-butyl) -phosphine-7-dirhodium was dissolved in pentane, and 5 g of dried silica gel were added. Was 12 hours stirred at room temperature and then decanted off the supernatant solution. After washing with pentane, the silica gel adsorbate was dried in vacuo.
Das Silicagel besaß eine Korngröße von 0,2 bis 0,5 mm. Die C/H-Analysen ergaben eine maximale Belegung von 240 mg (0,26 mMol) pro Gramm Adsorbat.The silica gel had a grain size of 0.2 to 0.5 mm. The C / H analyzes resulted in a maximum occupancy of 240 mg (0.26 mmol) per gram of adsorbate.
Beispiel 3 Katalytische Isomerisierung von Oct-1-en-3-ol zu Octan-3-ol mit Hilfe der Katalysatoren gemäß Beispiel 1 und 2 Ein Reaktionsgefäß, das mit einem Gaseinlaß und einem Magnetrührer ausgestattet war, wurde in einen Thermostaten eingesetzt, der auf 75 + 1 0C eingestellt wurde. Das Reaktionsgefäß wurde mit 2 bis 4 ml einer 0,78 M Lösung von Oct-1-en-3-ol in trockenem o-Xylol beschickt. Argon wurde über die gerührte Lösung geleitet, und die Temperatur ließ man einen konstanten Wert erreichen.Example 3 Catalytic isomerization of oct-1-en-3-ol to octan-3-ol with the help of the catalysts of Example 1 and 2 A reaction vessel with a Gas inlet and a magnetic stirrer was placed in a thermostat, which was set to 75 + 1 0C. The reaction vessel was filled with 2 to 4 ml of a 0.78 M solution of oct-1-en-3-ol in dry o-xylene charged. Argon was over the stirred solution passed and the temperature was allowed to remain constant reach.
Nach 20 Minuten wurde der jeweilige Katalysator in einem Molverhältnis zu dem Oct-1-en-3-ol von 10 2 in die Mitte des Reaktionsbehälters eingeführt. In Zeitabständen, die in der nachfolgenden Tabelle aufgeführt sind, wurden Proben von jeweils 2 bis 4 ul entnommen und mit einer 2 m langen Gasflüssigkeitschromatographiesäule analysiert, die mit 10% stabilisiertem DEGS auf Chromosorp P gepackt war und bei 950C arbeitete.After 20 minutes, each catalyst was in a molar ratio to the oct-1-en-3-ol of 10 2 introduced into the center of the reaction vessel. In The time intervals listed in the table below were samples of 2 to 4 µl each are removed and applied to a 2 m long gas-liquid chromatography column analyzed, which was packed with 10% stabilized DEGS on Chromosorp P and at 950C worked.
Die dabei erhaltenen Ergebnisse im Vergleich mit verschiedenen Katalysatoren, die aus Angewandte Chemie, 1980, Seite 60, bekannt sind, sind nachfolgend zusammengestellt.The results obtained in comparison with different catalysts, which are known from Angewandte Chemie, 1980, page 60, are summarized below.
Tabelle Katalysator Reaktions- Umwand- mittlere Reak- Bemerkungen zeit (min) lung(%) tionsgeschwindigkeit -1 (mMol-min ml Erfindung Beispiel 1 R=[C(CH3)3]3P 10 13,1 1,02 x 10-2 homogen R'=(CH2)2Si(OCH3)3 52 89,7 1,35 x 10-2 " 120 100 " Beispiel 2 R=C(CH3)3 7P 10 4,3 3,35 x 10 3 trägerfixie 3 ter Katalysator R'=(CH2)2SiO- 52 29,7 4,5 x 10 (silicagel) 1080 100 4,7 x 10 Stand der Technik R=ZC (CH3) 7P lo 4,6 3,6 x 10 3 homogen R'=C(CH3)3 55 32,9 4,7 x 10 990 67,6 5,3 x 10 3 Metallablagerung R=[C(CH3)3]P 10 >0,5 homogen R'=CH(CH3)2 115 3,0 2,0 x 10 990 36,0 2,8 x 10 R=[C(CH3)3]P 52 7,4 1,1 x 10 3 homogen R'=4-ClC6H4 120 18,8 1,2 x 10 " 1080 91 6,6 x 10 4 leichte Katalysatorzersetzung Die Vergleichsversuche in der Tabelle zeigen die überlegene Aktivität der erfindungsgemäßen Katalysatoren gemäß den aus dem Stand der Technik. bekannten Katalysatoren. Table Catalyst Reaction Conversion Average React Comments time (min) elation (%) rate -1 (mmol-min ml invention example 1 R = [C (CH3) 3] 3P 10 13.1 1.02 x 10-2 homogeneous R '= (CH2) 2Si (OCH3) 3 52 89.7 1.35 x 10-2 "120 100" example 2 R = C (CH3) 3 7P 10 4.3 3.35 x 10 3 supported 3rd catalyst R '= (CH2) 2SiO- 52 29.7 4.5 x 10 (silica gel) 1080 100 4.7 x 10 prior art R = ZC (CH3) 7P lo 4.6 3.6 x 10 3 homogeneous R '= C (CH3) 3 55 32.9 4.7 x 10 990 67.6 5.3 x 10 3 metal deposit R = [C (CH3) 3] P 10> 0.5 homogeneous R '= CH (CH3) 2 115 3.0 2.0 x 10 990 36.0 2.8 x 10 R = [C (CH3) 3 ] P 52 7.4 1.1 x 10 3 homogeneous R '= 4-ClC6H4 120 18.8 1.2 x 10 "1080 91 6.6 x 10 4 light Catalyst decomposition The comparative tests in the table show the superior activity of the catalysts of the invention according to the prior art of the technique. known catalysts.
Bei der Trägerfixierung nahm die Reaktionsgeschwindigkeit oegenüber der nichtträgerfixierten erfindungsgemäßen Komplexverbindung ab, lag aber immer noch erheblich günstiger als bei den bekannten Vergleichsverbindungen. Im übrigen könnte man bei trägerfixierten Katalysatoren selbst eine Abnahme der katalytischen Aktivität hinnehmen, da diese durch den Vorteil der Trägerfixierung kompensiert würde.When the support was fixed, the reaction rate increased the unsupported complex compound according to the invention from, but always lay considerably cheaper than the known comparison compounds. Furthermore In the case of supported catalysts, one could even see a decrease in the catalytic Accept activity, as this compensates for it through the advantage of the carrier fixation would.
Bei zwei der bekannten Vergleichskatalysatoren trat bei längerer Reaktionsdauer eine Katalysatorzersetzung auf, die das Reaktionsprodukt verunreinigt.In the case of two of the known comparative catalysts, the reaction time was prolonged decomposition of the catalyst which contaminates the reaction product.
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DE3101380A1 true DE3101380A1 (en) | 1982-10-21 |
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ID=6122818
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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DE19813101380 Withdrawn DE3101380A1 (en) | 1981-01-17 | 1981-01-17 | Organometal complex compounds, their preparation and their use |
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DE (1) | DE3101380A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0992505A2 (en) * | 1998-09-29 | 2000-04-12 | Degussa-Hüls Aktiengesellschaft | Sulfanyl silanes |
EP2602262A1 (en) * | 2011-12-07 | 2013-06-12 | Shin-Etsu Chemical Co., Ltd. | Organosilicon compound and method for preparing same, compounding agent for rubber, and rubber composition. |
-
1981
- 1981-01-17 DE DE19813101380 patent/DE3101380A1/en not_active Withdrawn
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0992505A2 (en) * | 1998-09-29 | 2000-04-12 | Degussa-Hüls Aktiengesellschaft | Sulfanyl silanes |
EP0992505A3 (en) * | 1998-09-29 | 2001-05-23 | Degussa AG | Sulfanyl silanes |
EP2602262A1 (en) * | 2011-12-07 | 2013-06-12 | Shin-Etsu Chemical Co., Ltd. | Organosilicon compound and method for preparing same, compounding agent for rubber, and rubber composition. |
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