Carbonylation of hydrocarbons via C-H activation catalyzed by RhCl(CO)(PMe sub 3 ) sub 2 under irradiation
- National Chemical Laboratory for Industry, Ibaraki (Japan)
- Mitsubishi Kasei Corporation, Yokohama (Japan)
C-H bonds in hydrocarbons are carbonylated into aldehydes by reaction with carbon monoxide in the presence of RhCl(CO)(PR{sub 3}){sub 2} under irradiation. The reaction proceeds at an ambient temperature under an atmospheric pressure of CO. The catalytic activity of RhCl(CO)(PR{sub 3}){sub 2} decreases in the order PMe{sub 3} {approx} 1,3,4-trimethylphospholane {approx} 1,3,4-trimethylphospholene > P(CH{sub 2}O){sub 3}CMe > PEt{sub 3} {approx} PBu{sub 3} > P(i-Pr){sub 3} {approx} P(OMe){sub 3} > dppe. The thiocyanato complex exhibits a similar catalytic activity to the chloro complex. The use of other complexes of Co, Ir, and Ru resulted in much lower catalytic activities. In the carbonylation of benzene, benzophenone and benzyl alcohol are formed as byproducts. The yield of benzaldehyde reached 3.3% on the basis of benzene. Monosubstituted benzenes are converted mainly to meta-substituted benzaldehydes. In the reaction of n-alkanes, a terminal methyl group is selectively carbonylated to give a linear aldehyde.
- OSTI ID:
- 5348182
- Journal Information:
- Journal of the American Chemical Society; (United States), Vol. 112:20; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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