- Metal-catalyzed reductive deamination of glutamic acid to bio-based dimethyl glutarate and methylamines
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Glutamic acid is a promising renewable platform molecule which is abundantly available in biomass waste streams; it is also efficiently manufactured by fermentation. Here we report the reductive deamination of glutamic acid to bio-based dimethyl glutarate and methylamines. In order to recycle nitrogen in an industrially relevant co-product, glutamic acid was modified to N,N-dimethylglutamic acid by a mild reductive alkylation with Pd/C. Subsequently, selective C-N hydrogenolysis in methanol resulted in dimethyl glutarate and trimethylamine. A wide screening of transition metals (Pt, Pd, Rh and Ru) immobilized on various supports showed that the highest yields of dimethyl glutarate were obtained with Pt/TiO2. An FTIR study and kinetic experiments on metal-loaded and unloaded supports demonstrate that the interplay between the metal and the moderate acidity of the support results in the excellent C-N hydrogenolysis activity and selectivity. Finally, reaction parameter optimization resulted in 81% yield of dimethyl glutarate with 1 wt% Pt/TiO2 at 225 °C, 30 bar H2 after 8 h.
- De Schouwer, Free,Cuypers, Thomas,Claes, Laurens,De Vos, Dirk E.
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supporting information
p. 1866 - 1876
(2017/06/09)
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- Oxidation of β-dicarbonyl compounds with tert-butyl hydroperoxide in the presence of vanadyl acetylacetonate
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Oxidation of β-dicarbonyl compounds with tert-butyl hydroperoxide in the presence of vanadyl acetylacetonate (benzene, 20°C) involves the activated methylene group with intermediate formation of trioxo derivatives and is accompanied by decomposition of carbon skeleton. The oxidation products are carbon dioxide, carboxylic acids, and tert-butyl and peroxy esters derived from the latter.
- Stepovik,Gulenova,Kalacheva,Potkina, A. Yu.
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scheme or table
p. 550 - 558
(2011/06/23)
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