The first case of competitive heterogeneously catalyzed hydrogenation using continuous-flow fixed-bed reactor system

Hydrogenation of binary mixtures of activated ketones on Pt-alumina and on Pt-alumina-cinchonidine catalysts

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Abstract

Under the experimental conditions of the Orito reaction the competitive hydrogenations of four binary mixtures of ethyl pyruvate (EP), methyl benzoylformate (MBF), pyruvic aldehyde dimethyl acetal (PA) and 2,2-diethoxyacetophenone (DAP) on unmodified Pt/Al 2O 3 (racemic hydrogenation) and catalyst modified by cinchonidine (chiral hydrogenation) were studied using continuous-flow fixed-bed reactor system (CFBR). Conversions of chiral and racemic hydrogenations were determined under 4 MPa H 2 pressure, at 293 K using toluene/acetic acid 9/1 as solvent. In the competitive chiral hydrogenation of MBF + EP and DAP + PA binary mixtures (S1 + S2) a new phenomenon was observed: namely the EP and PA are hydrogenated faster than MBF and DAP, whereas in racemic one the MBF and DAP are hydrogenated faster than the former ketones. The phenomenon verified for the first time in CFBR is dependent on the adsorption mode of the surface complexes of various compositions (S1-Pt, S2-Pt, S1-CD-Pt, S2-CD-Pt, CD = cinchonidine). In the chiral hydrogenation of DAP a rate decrease, i.e., "ligand deceleration" was observed instead of rate enhancement. Graphical Abstract: [Figure not available: see fulltext.]

Original languageEnglish
Pages (from-to)1616-1620
Number of pages5
JournalCatalysis Letters
Volume141
Issue number11
DOIs
Publication statusPublished - Nov 2011

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Aluminum Oxide
Binary mixtures
Ketones
Hydrogenation
Alumina
Catalysts
Pyruvaldehyde
Deceleration
Toluene
Aldehydes
Acetic acid
Acetic Acid
cinchonidine
Ligands
2,2-diethoxyacetophenone
Adsorption
phenylglyoxylic acid
Chemical analysis
ethyl pyruvate

Keywords

  • 2,2-Diethoxyacetophenone
  • Chiral and racemic hydrogenation
  • Cinchonidine
  • Continuous-flow reactor
  • Ethyl pyruvate
  • Methyl benzoylformate
  • Platinum
  • Pyruvic aldehyde dimethyl acetal

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

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title = "The first case of competitive heterogeneously catalyzed hydrogenation using continuous-flow fixed-bed reactor system: Hydrogenation of binary mixtures of activated ketones on Pt-alumina and on Pt-alumina-cinchonidine catalysts",
abstract = "Under the experimental conditions of the Orito reaction the competitive hydrogenations of four binary mixtures of ethyl pyruvate (EP), methyl benzoylformate (MBF), pyruvic aldehyde dimethyl acetal (PA) and 2,2-diethoxyacetophenone (DAP) on unmodified Pt/Al 2O 3 (racemic hydrogenation) and catalyst modified by cinchonidine (chiral hydrogenation) were studied using continuous-flow fixed-bed reactor system (CFBR). Conversions of chiral and racemic hydrogenations were determined under 4 MPa H 2 pressure, at 293 K using toluene/acetic acid 9/1 as solvent. In the competitive chiral hydrogenation of MBF + EP and DAP + PA binary mixtures (S1 + S2) a new phenomenon was observed: namely the EP and PA are hydrogenated faster than MBF and DAP, whereas in racemic one the MBF and DAP are hydrogenated faster than the former ketones. The phenomenon verified for the first time in CFBR is dependent on the adsorption mode of the surface complexes of various compositions (S1-Pt, S2-Pt, S1-CD-Pt, S2-CD-Pt, CD = cinchonidine). In the chiral hydrogenation of DAP a rate decrease, i.e., {"}ligand deceleration{"} was observed instead of rate enhancement. Graphical Abstract: [Figure not available: see fulltext.]",
keywords = "2,2-Diethoxyacetophenone, Chiral and racemic hydrogenation, Cinchonidine, Continuous-flow reactor, Ethyl pyruvate, Methyl benzoylformate, Platinum, Pyruvic aldehyde dimethyl acetal",
author = "G. Sz{\"o}llősi and Zsolt Makra and F. F{\"u}l{\"o}p and M. Bart{\'o}k",
year = "2011",
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language = "English",
volume = "141",
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TY - JOUR

T1 - The first case of competitive heterogeneously catalyzed hydrogenation using continuous-flow fixed-bed reactor system

T2 - Hydrogenation of binary mixtures of activated ketones on Pt-alumina and on Pt-alumina-cinchonidine catalysts

AU - Szöllősi, G.

AU - Makra, Zsolt

AU - Fülöp, F.

AU - Bartók, M.

PY - 2011/11

Y1 - 2011/11

N2 - Under the experimental conditions of the Orito reaction the competitive hydrogenations of four binary mixtures of ethyl pyruvate (EP), methyl benzoylformate (MBF), pyruvic aldehyde dimethyl acetal (PA) and 2,2-diethoxyacetophenone (DAP) on unmodified Pt/Al 2O 3 (racemic hydrogenation) and catalyst modified by cinchonidine (chiral hydrogenation) were studied using continuous-flow fixed-bed reactor system (CFBR). Conversions of chiral and racemic hydrogenations were determined under 4 MPa H 2 pressure, at 293 K using toluene/acetic acid 9/1 as solvent. In the competitive chiral hydrogenation of MBF + EP and DAP + PA binary mixtures (S1 + S2) a new phenomenon was observed: namely the EP and PA are hydrogenated faster than MBF and DAP, whereas in racemic one the MBF and DAP are hydrogenated faster than the former ketones. The phenomenon verified for the first time in CFBR is dependent on the adsorption mode of the surface complexes of various compositions (S1-Pt, S2-Pt, S1-CD-Pt, S2-CD-Pt, CD = cinchonidine). In the chiral hydrogenation of DAP a rate decrease, i.e., "ligand deceleration" was observed instead of rate enhancement. Graphical Abstract: [Figure not available: see fulltext.]

AB - Under the experimental conditions of the Orito reaction the competitive hydrogenations of four binary mixtures of ethyl pyruvate (EP), methyl benzoylformate (MBF), pyruvic aldehyde dimethyl acetal (PA) and 2,2-diethoxyacetophenone (DAP) on unmodified Pt/Al 2O 3 (racemic hydrogenation) and catalyst modified by cinchonidine (chiral hydrogenation) were studied using continuous-flow fixed-bed reactor system (CFBR). Conversions of chiral and racemic hydrogenations were determined under 4 MPa H 2 pressure, at 293 K using toluene/acetic acid 9/1 as solvent. In the competitive chiral hydrogenation of MBF + EP and DAP + PA binary mixtures (S1 + S2) a new phenomenon was observed: namely the EP and PA are hydrogenated faster than MBF and DAP, whereas in racemic one the MBF and DAP are hydrogenated faster than the former ketones. The phenomenon verified for the first time in CFBR is dependent on the adsorption mode of the surface complexes of various compositions (S1-Pt, S2-Pt, S1-CD-Pt, S2-CD-Pt, CD = cinchonidine). In the chiral hydrogenation of DAP a rate decrease, i.e., "ligand deceleration" was observed instead of rate enhancement. Graphical Abstract: [Figure not available: see fulltext.]

KW - 2,2-Diethoxyacetophenone

KW - Chiral and racemic hydrogenation

KW - Cinchonidine

KW - Continuous-flow reactor

KW - Ethyl pyruvate

KW - Methyl benzoylformate

KW - Platinum

KW - Pyruvic aldehyde dimethyl acetal

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U2 - 10.1007/s10562-011-0705-0

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M3 - Article

VL - 141

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JO - Catalysis Letters

JF - Catalysis Letters

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