Selective catalytic hydrogenation of 1-nitro-cyclohexene to cyclohexanone oxime in a high pressure continuous flow system

Eszter Varga, Attila Wootsch, Tamás Nagy, Ildikó Kovács, István Mándity, László Ürge, Ferenc Darvas

Research output: Chapter in Book/Report/Conference proceedingConference contribution

Abstract

Cyclohexanone oxime is the key intermediate of e-caprolactam synthesis. A new environmental friendly process, the selective hydrogenation of 1-nitro-cyclohexene, was optimized in a high pressure continuous flow reactor (H-Cube®) using different catalysts. The order of selectivity for obtaining cyclohexanone oxime was Pd < Rh < RuO2 < PtO2 < Ir < Au, that correlates perfectly with the width of the d-orbital of these metals. The best result yielding of cyclohexanone oxime (98%) was obtained on 1%Au/TiO2 at 70°C, 0.25 ml/min, and 70 bar H2 in ethanol. A 48-fold scale up was successfully achieved using H-Cube Midi™ (overall productivity: 150g/day). The reaction mechanism on gold catalyst was studied by hydrogenation of analogous compounds, intermediate trapping and deuteration. Deuteration of 1-nitro-cyclohexene resulted in pure syn-stereoisomer of cyclohexanone oxime, as proved by NMR. One step 1,4-hydrogenation was proposed as reaction mechanism on Au/TiO2. Furthermore, the method developed offers a new procedure for synthesis of syn-oximes, in general.

Original languageEnglish
Title of host publicationAmerican Chemical Society - 238th National Meeting and Exposition, ACS 2009, Abstracts of Scientific Papers
Publication statusPublished - Dec 1 2009
Event238th National Meeting and Exposition of the American Chemical Society, ACS 2009 - Washington, DC, United States
Duration: Aug 16 2009Aug 20 2009

Publication series

NameACS National Meeting Book of Abstracts
ISSN (Print)0065-7727

Other

Other238th National Meeting and Exposition of the American Chemical Society, ACS 2009
CountryUnited States
CityWashington, DC
Period8/16/098/20/09

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

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    Varga, E., Wootsch, A., Nagy, T., Kovács, I., Mándity, I., Ürge, L., & Darvas, F. (2009). Selective catalytic hydrogenation of 1-nitro-cyclohexene to cyclohexanone oxime in a high pressure continuous flow system. In American Chemical Society - 238th National Meeting and Exposition, ACS 2009, Abstracts of Scientific Papers (ACS National Meeting Book of Abstracts).