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Issue 5, 2013
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Pd/TOMPP-catalysed telomerisation of 1,3-butadiene with lignin-type phenols and thermal Claisen rearrangement of linear telomers

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Abstract

The Pd/TOMPP-catalysed (TOMPP = tris(2-methoxyphenyl)phosphine) telomerisation of 1,3-butadiene was studied under solvent- and base-free conditions with phenolic substrates that can be potentially derived from lignin. Large differences in catalytic activity were observed, with reactivity increasing in the order of phenol, p-cresol, guaiacol, creosol and syringol. This reactivity trend can be attributed to the substrates' relative nucleophilicities, as induced by the donating effects of the p-methyl and o-methoxy substituents. The chosen reaction conditions, i.e. temperature, ligand/metal and butadiene/substrate ratios, strongly influenced both the conversion and selectivity of the reaction. Remarkably, the composition of the reaction medium, i.e. the butadiene/substrate ratio, exerted a strong influence on the linear/branched ratio. High conversions and selectivities to the linear products are obtained when excess butadiene is used. The linear telomer products could be readily converted from O-alkylated to C-alkylated phenolics via the thermal Claisen rearrangement. High conversions and selectivities were observed after 2 hours at 200 °C. Branched o-octadienyl phenols were obtained in all cases except for the syringol telomer which gave the linear p-octadienyl product exclusively.

Graphical abstract: Pd/TOMPP-catalysed telomerisation of 1,3-butadiene with lignin-type phenols and thermal Claisen rearrangement of linear telomers

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Article information


Submitted
25 Jul 2012
Accepted
29 Oct 2012
First published
01 Nov 2012

Catal. Sci. Technol., 2013,3, 1215-1223
Article type
Paper

Pd/TOMPP-catalysed telomerisation of 1,3-butadiene with lignin-type phenols and thermal Claisen rearrangement of linear telomers

P. J. C. Hausoul, S. D. Tefera, J. Blekxtoon, P. C. A. Bruijnincx, R. J. M. Klein Gebbink and B. M. Weckhuysen, Catal. Sci. Technol., 2013, 3, 1215
DOI: 10.1039/C2CY20522J

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