Ag-0 and Co-0 nanocolloids as recyclable quasihomogeneous metal catalysts for the hydrogenation of alpha,beta-unsaturated aldehydes to allylic alcohol fragrances

作者：Mertens Pascal G N; Cuypers Frederic; Vandezande Pieter; Ye Xingpu; Verpoort Francis; Vankelecom Ivo F J; De Vos Dirk E^*

来源：Applied Catalysis A: General , 2007, 325(1): 130-139.

DOI：10.1016/j.apcata.2007.03.020

• selective hydrogenation
• unsaturated aldehyde
• allylic alcohol
• quasihomogeneous catalyst
• colloidal catalyst
• silver
• cobalt
• cinnamaldehyde
• citral
• leaf aldehyde
• membrane
• SRNF

The hydrogenation of the alpha,beta-unsaturated aldehydes cinnamaldehyde (trans-3-phenyl-2-propenal), citral (3,7-dimethyl-2,6-octadienal) and leaf aldehyde (trans-2-hexenal) was investigated with metal colloids as quasi homogeneous catalysts in organic solvents. Using polyvinylpyrrolidone-stabilized Ag-0 and Co-0 nanoclusters, the carbonyl compounds were chemoselectively hydrogenated to the desired allylic alcohol fragrances. Particularly the Ag-0 nanosols emerged as a worthwhile alternative for Pt or Ru based catalysts. Amides proved to be excellent solvents for the synthesis as well as for the application of the metal nanocolloids in the hydrogenation of alpha,beta-unsaturated aldehydes. In the challenging hydrogenation of citral, a selectivity exceeding 70% towards the doubly unsaturated alcohol isomers (geraniol and nerol) was attained at 90% conversion using Ag-0 nanocolloids dispersed in N,N-dimethylacetamide. Reactions were performed under mild conditions (2.0 MPa H-2, 323 K) at a molar citral/silver ratio of 200/1. The addition of Lewis acid cations, such as Fe3+ or Zn2+ resulted in a further improvement of the catalytic activity and chemoselectivity. Finally, by application of membrane filtrations, an efficient separation of the metallic nanocolloids from the reaction mixtures was realized. In the recycling of the metal nanosols, the metal catalysts' nanodispersion and performance were satisfactorily preserved.

• 出版日期2007-5-30