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Formation of dibenzofuran, dibenzo-p-dioxin and their hydroxylated derivatives from catechol
Journal article   Open access   Peer reviewed

Formation of dibenzofuran, dibenzo-p-dioxin and their hydroxylated derivatives from catechol

M. Altarawneh and B.Z. Dlugogorski
Physical Chemistry Chemical Physics, Vol.17(3), pp.1822-1830
2015
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Abstract

We present, in this study, mechanistic and kinetic accounts of the formation of dibenzofuran (DF), dibenzo-p-dioxin (DD) and their hydroxylated derivatives (OHs-DF/OHs-DD) from the catechol (CT) molecule, as a model compound for phenolic constituents in biomass. Self-condensation of two CT molecules produces predominantly a DD molecule via open- and closed-shell corridors. Coupling modes involving the o-semiquinone radical and the CT molecule (o-SQ/CT) generate two direct structural blocks for the formation of OHs-DF/OHs-DD structures, ether-type intermediates and di-keto moieties. The calculated reaction rate constants indicate that the fate of ether-type intermediates is to make hydroxylated diphenyl ethers rather than to undergo cyclisation reactions leading to the formation of preDF structures. Unimolecular loss of a H or OH moiety from a pivotal carbon in these hydroxylated diphenyl ethers then produces hydroxylated and non-hydroxylated DD molecules. Formation of OHs-DF initiated by o(C)–o(C) cross-linkages involving o-SQ/o-SQ and o-SQ/CT reactions incurs very similar reaction and activation enthalpies encountered in the formation of chlorinated DFs from chlorophenols.

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3 Agriculture, Environment & Ecology
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Chemistry, Physical
Physics, Atomic, Molecular & Chemical
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Chemistry
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