- MONOPHOSPHINE COMPOUNDS AND PALLADIUM CATALYSTS BASED THEREON FOR THE ALKOXYCARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS
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The invention relates to compounds of formula (I) where R1 is selected from —(C1-C12)-alkyl, —(C3-C12)-cycloalkyl, —(C3-C12)-heterocycloalkyl; R2 is selected from —(C3-C12)-heterocycloalkyl, —(C6-C20)-aryl, —(C3-C20)-heteroaryl; R3 is —(C3-C20)-heteroaryl; and R1, R2 and R3 may each independently be substituted by one or more substituents selected from —(C1-C12)-alkyl, —(C3-C12)-cycloalkyl, —(C3-C12)-heterocycloalkyl, —O—(C1-C12)-alkyl, —O—(C1-C12)-alkyl-(C6-C20)-aryl, —O—(C3-C12)-cycloalkyl, —S—(C1-C12)-alkyl, —S—(C3-C12)-cycloalkyl, —COO—(C1-C12)-alkyl, —COO—(C3-C12)-cycloalkyl, —CONH—(C1-C12)-alkyl, —CONH—(C3-C12)-cycloalkyl, —CO—(C1-C12)-alkyl, —COO—(C3-C12)-cycloalkyl, —N—[(C1-C12)-alkyl]2, —(C6-C20)-aryl, —(C6-C20)-aryl-(C1-C12)-alkyl, —(C6-C20)-aryl-O—(C1-C12)-alkyl, —(C3-C20)-heteroaryl, —(C3-C20)-heteroaryl-(C1-C12)-alkyl, —(C3-C20)-heteroaryl-O—(C1-C12)-alkyl, —COOH, —OH, —SO3H, —NH2, halogen. The invention further relates to Pd complexes comprising the compound according to the invention and to the use thereof in alkoxycarbonylation.
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Paragraph 0176; 0177; 0178; 0179; 0180; 0181
(2017/02/24)
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- PROCESS FOR PREPARING ESTERS FROM FORMATES AND OLEFINICALLY UNSATURATED COMPOUNDS
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The invention provides a process for preparing esters from formates and olefinically unsaturated compounds with catalysts based on palladium compounds. In addition, the invention discloses a polyphasic reaction mixture and nonyl methyl ester mixtures prepared by the process according to the invention.
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Paragraph 0042; 0050; 0060
(2014/10/29)
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- Photochemical Hydroformylation with Cobalt Catalysts in Methanol
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The photochemical hydroformylation of 1-octene with cobalt/phosphane complexes in methanol leads under mild conditions (80 deg C, 80 bar CO/H2) with >= 90percent selectivity to linear aldehydes.The reaction rate increases with temperature (Ea = 5 - 6 kcal/mol) and synthesis gas pressure, and is nearly independent of the cobalt source, e.g.Co(OAc)2, Co2(CO)8, or Co2(CO)6(PBu3)2.At low pressures hydroesterification is the preferred photoreaction of 1-octene.Isoprene reacts under similar conditions to give unsaturated oxoproducts and linear isoprene dimers.With unmodified octacarbonyldicobalt the hydroformylation of internal olefins is enhanced by UV light, but not the reaction of terminal olefins or dienes.UV irradiation of cobalt acetate under hydroformylation conditions leads to rapid reduction of the Co(II) species, thus decreasing the induction period from ca. 15 h (without irradiation) to ca. 30 min.
- Mirbach, Manfred J.,Topalsavoglou, Nikolaos,Phu, Tuyet Nhu,Mirbach, Marlis F.,Saus, Alfons
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p. 1422 - 1440
(2007/10/02)
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