Solvent effects in the enantioselective hydrogenation of ethyl benzoylformate

Gerson Martin, Päivi Mäki-Arvela, Dmitry Yu Murzin*, Tapio Salmi

*Korresponderande författare för detta arbete

Forskningsoutput: TidskriftsbidragArtikelVetenskapligPeer review

12 Citeringar (Scopus)

Sammanfattning

Solvent effects in the enantioselective hydrogenation of ethyl benzoylformate (EBF) to (R)-ethyl mandelate over (-)-cinchonidine (CD)-modified Pt/Al2O3 catalyst were studied in a semi-batch reactor. Solvents of different nature were used: protic (2-propanol, 1-propanol, 1-octanol and ethanol), aprotic polar (methyl acetate, acetone, ethyl acetate and tetrahydrofuran) and apolar solvents (methyl cyclohexane and toluene). The effects of pure solvents and binary solvent mixtures on hydrogenation rates and enantioselectivity were investigated. The highest enantiomeric excess (ee) of 72 % was obtained in ethyl acetate, decreasing nonlinearly with increasing dielectric constant (ε) being close to 20 % in ethanol. The highest value of the initial hydrogenation rate was obtained in the apolar solvents (21 mmol dm-3 min-1g cat -1) while the lowest one was observed in tetrahydrofuran (2 mmol dm-3 min-1 g cat -1). A kinetic model was proposed for the enantioselectivity dependence on dielectric constant based on Kirkwood treatment. The non-linear dependence of ee on (ε) was included in the model to describe quantitatively the variation of ee in different solvents. The results showed a good fit for ee as a function of ε.

OriginalspråkEngelska
Sidor (från-till)1051-1060
Antal sidor10
TidskriftCatalysis Letters
Volym143
Utgåva10
DOI
StatusPublicerad - okt 2013
MoE-publikationstypA1 Tidskriftsartikel-refererad

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