A series of variously substituted α,β-unsaturated methyl esters were hydrogenated with deuterium (deuteriumated) over deuterated Raney nickel, modified deuterated Raney nickel, and Pd/C. The deuterated Raney nickel catalysts were prepared by leaching Ni-Al alloy with NaOD in D2O. Each gram of deuterated Raney nickel can furnish approximately 45 to 50 m2L of D2 (STP), which is readily exchanged even from traces of atmospheric water. Deuterium distributions are similar for deuteriumations using either D2 or N2 gas overlaying reaction mixtures of deuterated Raney nickel and substrate in dioxane. However, N2produced less deuterium in the products because of atmospheric water contamination. L-glutamic acid modification of deuterated Raney nickel also produces less deuterium in the products, but deuterium distributions remain unchanged. Raney nickel does not catalyze simple 1,2-cis (syn) addition of deuterium across C=C double bonds but distributes deuterium among carbons contiguous to the double bonds. The distributions are influenced by structure and substituents; however, the results are adequately explained by the half-hydrogenated state mechanism.
ASJC Scopus subject areas
- Condensed Matter Physics
- Physical and Theoretical Chemistry
- Surfaces, Coatings and Films
- Materials Chemistry