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Download e-book for iPad: Advances in Organometallic Chemistry, Vol. 17: Catalysis and by F.G.A. Stone, Robert West (Eds.)

By F.G.A. Stone, Robert West (Eds.)

ISBN-10: 0080580181

ISBN-13: 9780080580180

ISBN-10: 0120311178

ISBN-13: 9780120311170

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Extra resources for Advances in Organometallic Chemistry, Vol. 17: Catalysis and Organic Syntheses

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This range was very critical, as were other reaction parameters. Rhodium alone gave the best yield of aldehyde (83%) at 60°C. Triphenylphosphine as cocatalyst induced the decomposition of the aldehyde product. For vinyl ethers, there again exists a strong preference for attachment of the formyl group to the carbon a to the oxygen atom. n-Butyl vinyl ether gave low yields of product, with the formyl group exclusively in the a position (4). Falbe and Korte (90) studied the cobalt hydroformylation of dihydropyran and its derivatives.

They also found that, provided the reaction rate was controlled by varying the concentration of olefin and of catalyst, the product composition varied only slightly as a function of either temperature or catalyst concentration. Results found are tabulated in Tables VII and VIII. 20 ROY L. 1 Benzene solvent; PHz,80 atm. 2. Phosphine-ModiJied Catalysts The introduction of alkyl phosphine complexes of cobalt carbonyl as hydroformylation catalysts was reported to have a significant effect on product composition (50, 51).

I 1. Further progress in providing linear aldehydes from olefinic substrates has been provided by modified rhodium catalysts. Without modifiers, the product from the hydroformylation has very low normal : is0 isomer ratios; I-octene gave only 31% of the linear isomers in one example (28). In an early investigation (28, 59, 60), critical combinations of several reaction parameters were discovered to produce unusually high yields of the linear isomer. The parameters included low partial pressure of carbon monoxide, high concentration of phosphite or aryl phosphine ligands, and low total gas pressure.

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Advances in Organometallic Chemistry, Vol. 17: Catalysis and Organic Syntheses by F.G.A. Stone, Robert West (Eds.)


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