2-Octanol catalytic hydrogenation

Similar equipment for applications on the laboratory scale has been reported (and has recently been commercialized) (69-72). Most of the reported applications had the aim of investigating kinetics of chemical reactions as indicated by changes in liquid-phase concentrations. The equipment can typically be used at elevated temperatures and pressures. Applications to heterogeneous catalytic reactions include investigations of the enantioselective hydrogenation of exocyclic a,p-unsaturated ketones catalyzed by Pd/C in the presence of (A)-proline (73) and the esterification of hexanoic acid with octanol catalyzed by a solid acid (the resin Nafion on silica) (74). 

Catalytic conversion of l-Octanol-2-d to ketone A quantity (29.7 ml.) of l-octanol-2-d was charged (space velocity 0.2) to a 5-mm. reactor tube containing 18 ml. of 8- to 10-mesh chromium oxide catalyst maintained at 400°. The 27.7 ml. of liquid product was fractionated in a concentric-tube etjlumn. A 60.6% yield of di-n-heptyl ketone was obtained. Approximately 17% of the alcohol was recovered "unconverted. Mass spectrometric analysis of the gaseous product showed the atomic ratio of deuterium to hydrogen to be 0.106. The molal yields of deuterium, hydrogen, and carbon monoxide produced per mole of ketone were 0.216, 2.040, and 0.815 respectively. 

Aqueous, two-phase catalysis is also utilized industrially in a number of other processes apart from hydroformylation. The hydrodimerization of butadiene and water, a telomerization variant yielding 1-octanol or 1,9-nonanediol (cf. Section 6.9), is carried out at a capacity of 5000 tonnes per annum by the Kuraray Corporation in Japan. Rhone-Poulenc is operating two-phase, aqueous, catalytic C—C coupling processes (using TPPTS obtained from Ruhrchemie) for small-scale production of various vitamin precursors such as geranylacetones. Moreover, TPPTS-modified Ru catalysts have been proposed for the homogeneously catalyzed hydrogenation to convert unsaturated ketones into saturated ones. 

NADP+ in a reaction with 2-propanol accompanied by formation of acetone as coproduct. Both ketone/alcohol reactions are equilibrium processes and therefore high 3delds of (f )-2-octanol are not available in a monophasic aqueous system, or in an organic-aqueous biphasic system where the partition coefficients of 2-propanol and acetone are approximately the same. It was found, however, that in a biphasic water/[bmim][(CF3S02)2N] system acetone was preferentially dissolved by the IL phase and this pulled the catalytic transfer hydrogenation of NADP+ by 2-propanol in the aqueous phase to near completion. Consequently, almost quantitative yields of (i )-2-octanol were obtained (275). 

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