Collection of Czechoslovak Chemical Communications - digital archive 

Abstract

Sixteen primary alcohols of the structure RCH₂OH (R = CH₃, C₂H₅, (CH₃)₂CH, (CH₃)₃CCH₂, HOCH₂, CH₃OCH₂, C₆H₅, C₆H₅CH₂, C₆H₅OCH₂, ClCH₂, BrCH₂, F₃C, CNCH₂, (CH₃)₂NCH₂, (C₂H₅)₂NCH₂ and tetrahydrofurfuryl) were explored for the possibility of obtaining the corresponding aldehydes by dehydrogenation on solid catalysts. Various catalysts were tested and two zinc oxide-chromium oxide catalysts were selected for further work because their activity and selectivity was satisfactory; moreover, the selectivity could be improved by addition of sodium into the catalysts and of water into the feed. The reaction was performed in the temperature range 250-450 °C and at atmospheric pressure. 2-Chloroethanol, 2-bromoethanol, ethylene glycol, 2-cyanoethanol and 2-(N,N-diethylamino)ethanol decomposed and deactivated the catalyst. The other alcohols were studied from the point of kinetics of dehydrogenation, which was described by a Langmuir-Hinshelwood type rate equation (3), and of substituent effects on rate, which were correlated by Taft equation (1) with the slope ρ = -1.46. The preparative value of catalytic dehydrogenation for obtaining substituted aldehydes was confirmed by prolonged runs and isolation of the aldehydic product by distillation using as the feeds 2-methoxyethanol and 2-(N,N-dimethylamino)ethanol, respectively.