No abstract

The commercial production of vanillin from sodium lignosulfonate under highly alkaline conditions, catalyzed by Cu2+ at elevated temperature and pressures up to ∼10 bar, has been simulated in a 3-L stirred reactor. Initially, the process was operated in the presence of nitrogen in dead-end mode, and it was shown that vanillin and vanillic acid were formed by hydrolysis at temperatures of 120, 140, and 160 °C. At the two higher temperatures, the amount of vanillin produced was the same. Subsequently, experiments were conducted at the same elevated pressures and temperatures with addition of air or oxygen-enriched air once the temperature in the reactor had reached temperatures similar to those used when only hydrolysis occurred. In this case, the concentration of vanillin at 140 and 160 °C was equal to that due to hydrolysis, and the subsequent 2-fold increase was due to oxidation. In addition, both vanillic acid and acetovanillone (which has rarely been reported) were produced, as was hydrogen. Thus, for the first time, it has been shown that the production of vanillin (and other compounds) from sodium lignosulfonate at elevated temperatures involves hydrolysis and oxidation, with hydrolysis starting at just above 100 °C, that is, much lower than has previously been reported. Approximately 50% is produced by each mechanism. In addition, the orders of the reactions of the different steps were estimated, and the reaction mechanisms are discussed.

Biotransformations of a series of ortho-, meta- and para-substituted ethylbenzene and propylbenzene substrates have been carried out, using Pseudomonas putida UV4, a source of toluene dioxygenase (TDO). The ortho- and para-substituted alkylbenzene substrates yielded, exclusively, the corresponding enantiopure cis-dihydrodiols of the same absolute configuration. However, the meta isomers, generally, gave benzylic alcohol bioproducts, in addition to the cis-dihydrodiols (the meta effect). The benzylic alcohols were of identical (R) absolute configuration but enantiomeric excess values were variable. The similar (2R) absolute configurations of the cis-dihydrodiols are consistent with both the ethyl and propyl groups having dominant stereodirecting effects over the other substituents. The model used earlier, to predict the regio- and stereo-chemistry of cis-dihydrodiol bioproducts derived from substituted benzene substrates has been refined, to take account of non-symmetric substituents like ethyl or propyl groups. The formation of benzylic hydroxylation products, from meta-substituted benzene substrates, without further cis-dihydroxylation to yield triols provides a further example of the meta effect during toluene dioxygenase-catalysed oxidations.

Hydrogenolysis of bark from three different species of tree using heterogeneous platinum group metal catalysts produces two major product streams. Aromatic substituted guaiacols are produced from lignin and the lignin-like regions of suberin and a range of saturated fatty acids and alcohols, including α,ω-functionalised species, are produced from the polyester regions of suberin. Control experiments demonstrate clear advantages of catalytic hydrogenolysis over base hydrolysis, both in terms of conversion and product selectivity.

Hydrogenolysis of cork has been examined using a range of precious metal catalysts studying the effect of the support, added base and solvent used.