DE2034908C2 - Addukt aus einem Ruthenium(II)-carboxylat und einem stabilisierenden Donorliganden - Google Patents
Addukt aus einem Ruthenium(II)-carboxylat und einem stabilisierenden DonorligandenInfo
- Publication number
- DE2034908C2 DE2034908C2 DE2034908A DE2034908A DE2034908C2 DE 2034908 C2 DE2034908 C2 DE 2034908C2 DE 2034908 A DE2034908 A DE 2034908A DE 2034908 A DE2034908 A DE 2034908A DE 2034908 C2 DE2034908 C2 DE 2034908C2
- Authority
- DE
- Germany
- Prior art keywords
- adduct
- ruthenium
- carboxylate
- donor ligand
- acetate
- 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.)
- Expired
Links
- 239000003446 ligand Substances 0.000 title claims description 3
- -1 ruthenium (II) carboxylate Chemical class 0.000 title claims description 3
- 230000000087 stabilizing effect Effects 0.000 title claims 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 11
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 6
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QMMOXUPEWRXHJS-HYXAFXHYSA-N (z)-pent-2-ene Chemical compound CC\C=C/C QMMOXUPEWRXHJS-HYXAFXHYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 150000001336 alkenes Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 1
- ZYECOAILUNWEAL-NUDFZHEQSA-N (4z)-4-[[2-methoxy-5-(phenylcarbamoyl)phenyl]hydrazinylidene]-n-(3-nitrophenyl)-3-oxonaphthalene-2-carboxamide Chemical compound COC1=CC=C(C(=O)NC=2C=CC=CC=2)C=C1N\N=C(C1=CC=CC=C1C=1)/C(=O)C=1C(=O)NC1=CC=CC([N+]([O-])=O)=C1 ZYECOAILUNWEAL-NUDFZHEQSA-N 0.000 description 1
- CGHIBGNXEGJPQZ-UHFFFAOYSA-N 1-hexyne Chemical compound CCCCC#C CGHIBGNXEGJPQZ-UHFFFAOYSA-N 0.000 description 1
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 1
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000004435 EPR spectroscopy Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- MJOQJPYNENPSSS-XQHKEYJVSA-N [(3r,4s,5r,6s)-4,5,6-triacetyloxyoxan-3-yl] acetate Chemical compound CC(=O)O[C@@H]1CO[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O MJOQJPYNENPSSS-XQHKEYJVSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- WPYMKLBDIGXBTP-VQEHIDDOSA-N benzoic acid Chemical compound OC(=O)C1=CC=C[13CH]=C1 WPYMKLBDIGXBTP-VQEHIDDOSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000005292 diamagnetic effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- WJIBZZVTNMAURL-UHFFFAOYSA-N phosphane;rhodium Chemical compound P.[Rh] WJIBZZVTNMAURL-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 description 1
- 239000004324 sodium propionate Substances 0.000 description 1
- 235000010334 sodium propionate Nutrition 0.000 description 1
- 229960003212 sodium propionate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
-
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- 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
- B01J31/1805—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 nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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- 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
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- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
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- 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
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
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- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
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- B01J2531/0213—Complexes without C-metal linkages
- B01J2531/0219—Bimetallic complexes, i.e. comprising one or more units of two metals, with metal-metal bonds but no all-metal (M)n rings, e.g. Cr2(OAc)4
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- Y10S585/00—Chemistry of hydrocarbon compounds
- Y10S585/8995—Catalyst and recycle considerations
- Y10S585/906—Catalyst preservation or manufacture, e.g. activation before use
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- Chemical & Material Sciences (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
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- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Pyridine Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Description
Die einzigen bisher bekannten genau definierten
Rutheniumcarboxylate sind diejenigen vom Typ Ru2(OCOR)1Cl, welche mit einem Ru(II)-Atom und
einem Ru(III)-Atom oder mit zwei äquivalenten Ru-Atomen des Oxidationszustandes 2,5 formuliert
werden können.
Die Erfindung hat sich die Aufgabe gestellt. Katalysatoren zu schaffen, welche in der Lage sind,
olefinische zu hydrierende Substrate, die in Benzol/Alkohol-Mischungen
unlöslich oder nur bedingt löslich sind, in einem vollständig polaren Medium zu hydrieren.
Diese Aufgabe wird durch die Erfindung durch Addukte gemäß dem Patentanspruch gelöst.
Die erfindungsgemäßen Addukte sind in polaren Lösungsmitteln vollständig löslich. In dieser Beziehung
sind sie anderen ähnlichen Katalysatoren, wie RhCl(PPh3J3. RhH(COXPPh3)3 oder RuH(OXPPh3J3
überlegen, da sie im Gegensatz zu diesen bekannten katalysatoren in der Lage sind, olefinische zu
hydrierende Substrate, die in Benzol/Alkohol-Mischungen unlöslich oder nur bedingt löslich sind, in einem
vcilsiändig polaren Medium zu hydrieren.
Die erfindungsgemäßen Addukte sind sehr spezifische Katalysatoren. So wird Hex-1-en, ein endständiges
Olefin, bei ihrem Einsatz in ausgeprägtem Umfange hydriert, während keine Hydrierung im Falle von
cis-Pent-2-en oder Cyclohexen, d.h. inneren Olefinen, festzustellen ist. Hex-1-in wird langsam hydriert,
allerdings unter einem niederen H2-Partialdruck. In jedem Falle ist es möglich, selektiv Hex-1-en in einer
Mischung, die auch Cyclohexen und/oder cis-Pent-2-en sowie Hex-1-in enthält, zu hydrieren.
Ferner ist eine Selektivität bezüglich der Hydrierung nichtkonjugierter Diene sowie nichtkonjugierter und
konjugierter Diene erwähnenswert. Außerdem wird im Falle von Propargylalkohol oder Allyiphenylether keine
Hydrierung beobachtet.
Nachfolgend wird die Erfindung näher erläutert:
Herstellung von Dirutheniumtetraacetat
(Durethenium-u-t-acetat)
(Durethenium-u-t-acetat)
Eine Lösung von 2 g hydratisiertem Rutheniumtrichlorid und 4 g Natriumacetattrihydrat in 50 ml Eisessig
und 50 ml Ethanol wurde unter Rückfluß gekocht, woraufhin die rotviolette Farbe nach 4 h in dunkles
Grün umschlug und der Feststoff mit der minimalen Menge eines absoluten Ethanols extrahiert und die
unlöslichen Natriumsalze abfiltriert wurden. Die Eindampfung
des Filtrates ergab einen grün-schwarzen Feststoff, welcher kein Chlorid enthielt und bei der
Analyse annähernd Ru2(OCOMe)4 ergab;
gefunden:
C = 22.9%; H =3,5%;
berechnet: (ChHi2O8Ru2):
berechnet: (ChHi2O8Ru2):
C = 2I.8%; 11 = 2.7%.
Das Produkt ist in Wasser und in Alkoholen löslich, und in Anwesenheit von Phenol löst es sich in Benzol,
Aceton, CCL1 und CHCl3, in denen es normalerweise
unlöslich ist, auf.
' Diruthenium(II)-u^-acetat-bis-(triphenylphosphin)
und -bis(pyridin)
und -bis(pyridin)
Zu dem grün-schwarzen Acetat in Methanol wurde ein Überschuß einer gesättigten methanolischen Lösung
ίο von Triphenylphosphin bei Zimmertemperatur gegeben.
Nach dem Stehen über Nacht wurden die grünen Kristalle des Adduktes gesammelt, mit kaltem Methanol
gewaschen und in einem Stickstoffstrom getrocknet. Das Produkt wurde aus Benzol/Methanol umkristallisiert.
Ausbeute etwa 70%, bezogen auf den Rutheniumgehalt von RuCl3 · aq.:Zersetzung= 183°C.
Analyse:
gefunden:
gefunden:
C = 54,5%. H =4,6%; P = 6,3%.
Molekulargewichtsbestimmung in Benzol = 960.
Empirische Formel: CkH42O3P2Ru2 entsprechend:
Molekulargewichtsbestimmung in Benzol = 960.
Empirische Formel: CkH42O3P2Ru2 entsprechend:
C=54,8%; H =4,4%; P = 6,4%
sowie einem Molekulargewicht von 963.
sowie einem Molekulargewicht von 963.
Messungen der Suszeptibilität nach der Methode von Guoy und die übliche Korrektur für den Diamagnetismus
der Liganden zeigte, daß der Komplex diamagnetisch ist. Der Festkörper gab nur ein sehr schwaches
Signal bei der Elektronenspinresonanz; dieses kann einer Spur einer paramagnetischen Verunreinigung
zugeschrieben werden.
Die Zugabe von Pyridin zu einer methanolischen Lösung des Acetates nach einer analogen Methode zu
der oben für das PPIvj-Addukt beschriebenen ergab das
entsprechende Pyridin-Addukt als dunkelblaue Kristal-
Zu 035 g des grün-schwarzen Acetats in 5 ml Methanol wurde 1 ml Pyridin unter einer Stickstoffatmosphäre
zugesetzt. Die Lösung wechselte die Farbe von grün zu tiefblau, und nach der Abkühlung auf 5° C
für mehrere Stunden wurden dunkelblaue Kristalle des Adduktes abgeschieden. Diese wurden abfiltriert, mit
einer minimalen Menge an Methanol gewaschen und unter Stickstoff getrocknet.
Das Addukt verlor rasch Pyridin, selbst wenn es unter
einer Stickstoffatmosphäre gehalten wurde. Zersetzung: etwa 2500C.
Analyse:
gefunden:
gefunden:
C = 34.8%/34,6%; H = 3,4%/3.5%; ί·ί = 4.6%/4,7%.
Der empirischen Formel Ci8H22N2O8Ru2 entsprechen:
C = 363%; H =3,7%; N =4,7%.
Die Einwirkung von Protonen auf diese Rutheniumverbindungen, insbesondere durch eine starke Säure, ergibt Stoffe, welche extrem aktive Katalysatoren für Hydrierungsreaktionen darstellen.
Die Einwirkung von Protonen auf diese Rutheniumverbindungen, insbesondere durch eine starke Säure, ergibt Stoffe, welche extrem aktive Katalysatoren für Hydrierungsreaktionen darstellen.
Die Säurebehandlung einer Lösung des Adduktes Ru2(OCOMe4) · 2 PPh3 in Methanol in Abwesenheit
von überschüssigem Triphenylphosphin mit wäßriger Fluoroborsäure ergab einen Stoff, welcher die Hydrierung
von Hex-1 -en stark katalysierte.
Das mit Protonen behandelte Acetat oder Addukt des Acetates ist ein äßerst selektiver Katalysator. So wird
mit cis-Pent-2-en und anderen inneren Alkenen, z.B.
Cyclohexen. keine Hydrierung beobachtet. In dieser Hinsicht scheint der Katalysator viel stärker selektiv als
der entsprechende Rhodiumphosphinkatalysator zu sein. Die Selektivität tritt ebenfalls zwischen cyclischen,
3 4
nicht konjugierten Dienen auf. wobei CycIoocta-1,5- Propionsäure anstelle von Natriumacetat und Essigsäu-
dien sehr rasch hydriert wird, im Gegensatz zu der re erhalten werden. Ebenfalls kann das Benzoat auf
geringen Geschwindigkeit bei BicycIo(2il)hepta-2,5- analoge Weise mittels Natriumbenzoat und Benzoesäu-
dien. re erhalten werden.
Das Propionat kann mit Natriumpropionat und 5
Claims (1)
- Patentanspruch:Addukt aus einem Ruthenium(II)-carboxyIat und einem stabilisierenden Donorliganden A der allgemeinen Formel Ru2(OCOR)4-A2, in der R für die Reste Methyl-, Äthyl- und Phenyl- steht und A Pyridin oder Triphenylphosphin bedeutet.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB3524969 | 1969-07-14 |
Publications (2)
Publication Number | Publication Date |
---|---|
DE2034908A1 DE2034908A1 (de) | 1971-01-28 |
DE2034908C2 true DE2034908C2 (de) | 1983-08-25 |
Family
ID=10375578
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE2034908A Expired DE2034908C2 (de) | 1969-07-14 | 1970-07-14 | Addukt aus einem Ruthenium(II)-carboxylat und einem stabilisierenden Donorliganden |
DE2034909A Expired DE2034909C3 (de) | 1969-07-14 | 1970-07-14 | Ruthenium, Rhodium oder Molybdän enthaltender Katalysator sowie seine Verwendung als Hydrierungskatalysator |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE2034909A Expired DE2034909C3 (de) | 1969-07-14 | 1970-07-14 | Ruthenium, Rhodium oder Molybdän enthaltender Katalysator sowie seine Verwendung als Hydrierungskatalysator |
Country Status (6)
Country | Link |
---|---|
US (2) | US3748332A (de) |
JP (2) | JPS518927B1 (de) |
DE (2) | DE2034908C2 (de) |
FR (2) | FR2055059A5 (de) |
GB (1) | GB1326012A (de) |
NL (2) | NL172303C (de) |
Families Citing this family (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3939219A (en) * | 1969-07-14 | 1976-02-17 | Johnson, Matthey & Co., Limited | Hyrogenation of unsaturated compounds |
US3948999A (en) * | 1973-08-13 | 1976-04-06 | Universal Oil Products Company | Hydroformylation of an unsaturated compound |
US3974196A (en) * | 1973-11-28 | 1976-08-10 | Japan Synthetic Rubber Co., Ltd. | Method for disproportionating ethylenically unsaturated compounds having functional ester groups |
US3962131A (en) * | 1975-01-28 | 1976-06-08 | Pfizer Inc. | Rhodium containing catalyst and use thereof in preparation of 6-deoxy-5-oxytetracycline |
US4039585A (en) * | 1975-09-08 | 1977-08-02 | Uop Inc. | Hydroformylation process |
US4102920A (en) * | 1977-01-13 | 1978-07-25 | Air Products & Chemicals, Inc. | Production of carboxylic acids and esters |
US4313893A (en) * | 1978-12-26 | 1982-02-02 | Standard Oil Company | Carbonylation of olefinically unsaturated compounds |
US4246177A (en) * | 1979-06-21 | 1981-01-20 | Phillips Petroleum Company | Preparation of dihydropyrans |
US4266085A (en) * | 1979-08-13 | 1981-05-05 | Shell Oil Company | Olefin disproportionation process |
US4273936A (en) * | 1979-09-28 | 1981-06-16 | Union Carbide Corporation | Rhodium-catalyzed oxidation process for producing carboxylic acids |
US4652677A (en) * | 1980-03-10 | 1987-03-24 | The Standard Oil Company | Selective hydrocarboxylation of propylene to isobutyric acid |
US4417077A (en) * | 1980-10-01 | 1983-11-22 | University Of Illinois Foundation | Heterogeneous anionic transition metal catalysts |
NL8204883A (nl) * | 1982-12-17 | 1984-07-16 | Shell Int Research | Werkwijze voor de bereiding van carbonzuuranhydriden. |
US4863892A (en) * | 1983-08-16 | 1989-09-05 | Phillips Petroleum Company | Antifoulants comprising tin, antimony and aluminum for thermal cracking processes |
US4544789A (en) * | 1983-09-06 | 1985-10-01 | University of Illinois Board of Trustees | Stereoselective synthesis of internal olefins |
US4806678A (en) * | 1983-10-13 | 1989-02-21 | Texaco Inc. | Process for the hydroformylation of allylic esters using a cobalt catalyst |
JPS62265293A (ja) * | 1986-05-13 | 1987-11-18 | Takasago Corp | ルテニウム−ホスフイン錯体 |
US4704377A (en) * | 1986-05-19 | 1987-11-03 | Ethyl Corporation | Metathesis of acetylenes |
JPS63145291A (ja) * | 1986-12-09 | 1988-06-17 | Takasago Corp | ルテニウム−ホスフイン錯体 |
US4981973A (en) * | 1988-06-30 | 1991-01-01 | Union Carbide Chemicals And Plastics Company, Inc. | Transvinylation reaction |
US5155253A (en) * | 1988-06-30 | 1992-10-13 | Union Carbide Chemicals & Plastics Technology Corporation | Transvinylation process for the preparation of thermally labile vinyl compounds and for vinyl compounds prepared from thermally labile acids |
DE3921263A1 (de) * | 1989-06-29 | 1991-01-24 | Bayer Ag | Verfahren zur selektiven hydrierung nitrilgruppenhaltiger olefine |
US5149854A (en) * | 1990-12-10 | 1992-09-22 | Mooney Chemicals, Inc. | Preparation of platinum group metal and rhenium carboxylates |
US5210207A (en) * | 1991-01-31 | 1993-05-11 | Union Carbide Chemicals & Plastics Technology Corporation | Transvinylation process by reactive distillation |
US5202472A (en) * | 1991-06-17 | 1993-04-13 | Ethyl Corporation | Asymmetric hydrogenation of aromatic-substituted olefins using organonickel catalyst |
US5190905A (en) * | 1991-06-17 | 1993-03-02 | Ethyl Corporation | Asymmetric hydrogenation of aromatic-substituted olefins using metal or metal alloy catalysts |
US5187281A (en) * | 1991-06-17 | 1993-02-16 | Ethyl Corporation | Asymmetric hydrogenation of aromatic-substituted olefins using organoiridium catalyst |
US5187136A (en) * | 1991-06-17 | 1993-02-16 | Ethyl Corporation | Asymmetric hydrogenation of aromatic-substituted olefins using organorhenium catalyst |
US5191095A (en) * | 1991-06-17 | 1993-03-02 | Ethyl Corporation | Asymmetric hydrogenation of olefinic amides using organoruthenium catalyst |
US5177231A (en) * | 1991-06-17 | 1993-01-05 | Ethyl Corporation | Asymmetric hydrogenation of aromatic-substituted olefins using cationic ruthenium(III) complexes |
US5198576A (en) * | 1991-08-26 | 1993-03-30 | Ethyl Corporation | Bicyclooctyl phosphines and catalysts thereof |
FR2730229B1 (fr) * | 1995-02-02 | 1997-04-11 | Rhone Poulenc Chimie | Procede de preparation de carboxylates d'iridium et leur utilisation comme catalyseurs |
US6812184B1 (en) | 1996-06-17 | 2004-11-02 | Exxonmobil Chemical Patents Inc. | Supported late transition metal catalyst systems |
GB0427821D0 (en) * | 2004-12-17 | 2005-01-19 | Bp Chem Int Ltd | Catalyst and process |
JP5343483B2 (ja) * | 2008-09-24 | 2013-11-13 | Jsr株式会社 | 化学気相成長材料および化学気相成長方法 |
JP5343482B2 (ja) * | 2008-09-24 | 2013-11-13 | Jsr株式会社 | 化学気相成長方法 |
US8957235B2 (en) | 2011-12-12 | 2015-02-17 | Chevron Phillips Chemical Company Lp | Preparation of transition metal carboxylates |
US9956548B2 (en) | 2011-12-12 | 2018-05-01 | Chevron Phillips Chemical Company Lp | Preparation of an olefin oligomerization catalyst |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1121642A (en) * | 1965-02-18 | 1968-07-31 | Ici Ltd | New organic rhodium complexes and uses thereof |
BE598298A (de) * | 1959-10-06 | 1900-01-01 | ||
US3366646A (en) * | 1965-06-23 | 1968-01-30 | Shell Oil Co | Hydrogenation process |
GB1197723A (en) * | 1966-07-12 | 1970-07-08 | Johnson Matthey Co Ltd | Improvements in and relating to Catalysts. |
FR1537041A (fr) * | 1967-06-29 | 1968-08-23 | Rhone Poulenc Sa | Nouveaux complexes du ruthénium et procédés pour leur obtention |
US3562181A (en) * | 1967-07-19 | 1971-02-09 | Du Pont | Supported catalysts for dimerization of acrylonitriles and process of using the same |
US3511885A (en) * | 1967-12-11 | 1970-05-12 | Phillips Petroleum Co | Olefin conversion and catalyst therefor |
GB1258045A (de) * | 1967-12-22 | 1971-12-22 | ||
US3558517A (en) * | 1969-03-24 | 1971-01-26 | Phillips Petroleum Co | Complexes of fe,ru,os,rh or ir with organoaluminums as olefin reaction catalysts |
US3542751A (en) * | 1969-04-09 | 1970-11-24 | Goodyear Tire & Rubber | Production of cis-1,4-polydienes by means of a ternary catalyst system |
-
1969
- 1969-07-14 GB GB3524969A patent/GB1326012A/en not_active Expired
-
1970
- 1970-07-07 US US00053032A patent/US3748332A/en not_active Expired - Lifetime
- 1970-07-07 US US00053031A patent/US3725305A/en not_active Expired - Lifetime
- 1970-07-10 FR FR7025839A patent/FR2055059A5/fr not_active Expired
- 1970-07-10 FR FR7025841A patent/FR2055060A5/fr not_active Expired
- 1970-07-13 NL NLAANVRAGE7010315,A patent/NL172303C/xx not_active IP Right Cessation
- 1970-07-14 DE DE2034908A patent/DE2034908C2/de not_active Expired
- 1970-07-14 NL NLAANVRAGE7010375,A patent/NL170924C/xx not_active IP Right Cessation
- 1970-07-14 DE DE2034909A patent/DE2034909C3/de not_active Expired
- 1970-07-14 JP JP45061085A patent/JPS518927B1/ja active Pending
- 1970-07-14 JP JP45061084A patent/JPS5023393B1/ja active Pending
Non-Patent Citations (1)
Title |
---|
NICHTS-ERMITTELT |
Also Published As
Publication number | Publication date |
---|---|
NL170924B (nl) | 1982-08-16 |
DE2034908A1 (de) | 1971-01-28 |
NL7010315A (de) | 1971-01-18 |
US3748332A (en) | 1973-07-24 |
FR2055059A5 (de) | 1971-05-07 |
DE2034909C3 (de) | 1980-04-03 |
GB1326012A (en) | 1973-08-08 |
JPS5023393B1 (de) | 1975-08-07 |
US3725305A (en) | 1973-04-03 |
JPS518927B1 (de) | 1976-03-22 |
FR2055060A5 (de) | 1971-05-07 |
NL172303C (nl) | 1983-08-16 |
DE2034909A1 (de) | 1971-01-28 |
DE2034909B2 (de) | 1979-06-21 |
NL170924C (nl) | 1983-01-17 |
NL172303B (nl) | 1983-03-16 |
NL7010375A (de) | 1971-01-18 |
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