Petroleum Chemistry, Vol.43, No.6, 375-378, 2003
Hydrocarbobutoxylation of heptene-1 catalyzed by a Pd(0) complex in the presence of methanesulfonic acid
The reaction of 1-heptene with CO and 1-butanol catalyzed by Pd(dba)(2) (dba is dibenzylideneacetone) in the presence of methanesulfonic acid and tertiary phosphine (PR3) was studied. The dependences of the reaction yield and regioselectivity on the solvent type, CO pressure, amount of PR3, and its structure were elucidated. It was found that at R = 94% Ph the catalyst was the most active in butanol (96 h(-1)) and toluene (72 h(-1)), whereas the selectivity for the linear product (S) had the highest value in dioxane (92%). The dependence of the product yields on CO pressure is nonmonotonic in character. The catalyst properties are virtually independent of the amount of PPh3. Ligands PR3, where R is a substituted phenyl, decrease the catalyst activity; a high S value was observed in the case of R = 4-ClC6H4: 92% in toluene and 94% in butanol. The reaction mechanism is discussed in relation to the results obtained.