Read e-book online Advances in Organometallic Chemistry, Vol. 17: Catalysis and PDF

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

Example text

Each of these base materials was then functionalized by the reactions shown in Eq. (49). \ \ KPPh, THF , (49) \ The catalyst formed in this manner exhibited carbonyl infrared absorptions, as shown in Table XXX. These catalysts were tested by hydroformylation of ethylene or propylene at 100°C and atmospheric pressure. Both were effective, with (A) being better than (B), probably because of the higher surface area. The aldehyde formed from propylene was a mixture of 63% n- and 37% isobutyraldehyde.

Small amounts gave low reaction rates, whereas excessive loading caused blockage of the pores in the silica gel and reduced the effective surface area, again causing decreased rates. Thus, conversion as a function of loading passed through a maximum. Reaction conditions were 148°C and 700 psi. 7: 1 were obtained, even with excess triphenylphosphine present. Investigations have shown that polymer-bound rhodium hydroformylations respond to reaction parameters in a manner similar to the homogeneous counterparts, although some departures occur (114).

In the absence of ligand, the reaction would not proceed at the cited conditions of temperature and pressure; slightly more severe conditions were required. Table reprinted with permission from J . Org. Chem. 34, 327 (1969). Copyright by the American Chemical Society. 25 Hydroformylation T A B L E XI11 HYDROFORMYLATION OF 1-OCTENE WITH VARIOUS Hz/CO RATIOS"(5'9) RhiC (g) Reaction time (min) % Aldehyde which H,/CO Ratio Iil 311 113 15 10 10 30 30 60 86 90 75 is straight-chain 'I Octene, 112 g ; 5% RhlC.

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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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