| Budget Amount *help |
¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 1998: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1997: ¥2,400,000 (Direct Cost: ¥2,400,000)
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| Research Abstract |
A wide variety of solid base catalysts were prepared, and examined their catalytic properties for dimerization of methyl crotonate, addition of nitromethane to usnsaturated carbonyl compounds, and cyanoethylation of alcohols with acrylonitrile for developing hetergenous catalysts active for Michael addition reactions which are important organic synthesis forming C-C bonds.
For dimerization of methyl crotonate, only MgO exhibited a high activity among solid bases examined. The reaction is initiated by abstraction of allylic proton by basic sites to form an anionic intermediate which attacks beta-position C atom of a second methyl crotonate. The reaction completes by double bond migration as a final step. A high activity of MgO is suggested to be due to a moderate absorptivity and high density of active sites.
For Michael additions of nitromethane to <encircledR>-unsaturated compounds, KF/alumina and KOH/alumina exhibited a high activity, The reaction mechanisms were elucidated, and the reactivity of reactant depended on the charge denstiy of beta-carbon of the reactant
For cyanoethylation of alcohols with acrylonitrile, alkaline earth hydroxides and oxides, KF/alumina, KOH/alumina, and rare earth oxides exhibited a high activity. The reaction rate are determined by a combination of acidity of alcohol with basic strength of active sites. An alcohol of high acidity reacts faster on a weakly basic catalyst
For the reactions involving alcohols, a solid based catalyst is scarcely poisoned by water vapor and carbon dioxide, which is caused by a strong interaction of alcohols with basic sites on the catalysts.
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