Catalysis of Organic..

36Halophosphite LigandsTable 2 Temperature Effects on Butyraldehyde ProductionRun a Ligand Temperature,o CN/I RatioCatalystActivity b1 2 95 5.0 3.72 2 105 3.9 6.03 2 115 3.8 6.2a All runs conducted at 260 psig and specified temperature utilizing 7.7 mg of Rh,190 mL of DOP, 1.2 grams of ligand with 1:1 H 2 /CO and 54 psia C 3 H 6b Catalyst activity is expressed as kilograms of butyraldehyde per gram-Rh-hour.The effect of the hydrogen to carbon monoxide molar ratios in the feed gas tothe reaction is significant. Changes in the feed gas ratio will strongly affect theequilibrium of Equation 1 and thus impact the performance and selectivity of thecatalyst. A series of bench unit runs were performed and the data is summarized inTable 3.Table 3 Reactant Partial Pressure EffectsRun a Ligand H 2 /CO Ratio N/I CatalystActivity b1 10 0.5:1 4.5 1.432 10 1:1 5.9 2.133 10 2:1 7.2 1.63a All runs at 115 o C, 260 psig utilizing 15 mg Rh, 2.06 grams of ligand in 190 mL ofDOP with a C 3 H 6 partial pressure of 54 psia.b Catalyst activity is expressed as kilograms of butyraldehyde per gram-Rh-hour.The hydroformylation capabilities of halophosphite catalysts are not limited topropylene or alpha olefins. A variety of other olefins have been examined andrepresentative examples are presented in Table 4.Table 4 Hydroformylation of Various OlefinsRun a Ligand Substrate Products Ratio1 1 MethylMethacrylateMethyl isobutyrate,Methyl(2-methyl-3-formyl)propionate, &methyl (2-methyl-2-formyl)propionateL/B = 2.63