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

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

ISBN-10: 0120311178

ISBN-13: 9780120311170

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

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Fell and Bahrmann (97) explored the effects on reaction rate and product distribution of trialkylphosphines and phospholanes with varying steric and electronic effects. The ligand cone angle (9 8) was used as a measure of steric bulk, and for electronic effects the Z x ( i ) value was chosen. The results indicated that neither o f these two criteria was exclusively responsible for the catalytic activity of the phosphine-substituted catalysts. Triisopropylphosphine gave the highest reaction rate, a high overall yield.

The hydroformylation was conducted at 140°C and 300 atm, followed by hydrogenation and cyclization at 200"-24O"C, Eq. (33). CH$H =CHCOOC ,H -[ CH,CHC H,COOC,H, I CHO + CH,C H,CH,COOC ,H5 I CHO 1 With rhodium catalysts, higher amounts of the lactone which is formed 36 ROY L. PRUETT from the p-formylated product (13) were observed (70), as shown in Table XXIII. At the lowest temperature, appreciable amounts of the aisomer were noted. At the higher temperatures, y-formylation resulting from isomerization was noted, although the quantity was much less significant than that found with cobalt catalyst.

25 20 25 65 80 Substrate, I-hexene; temperature, 100°C; pressure, 1000-2000 psi 2/1 H,/ co.

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