Synthesis 2006(15): 2523-2530  
DOI: 10.1055/s-2006-942434
PAPER
© Georg Thieme Verlag Stuttgart · New York

Synthesis of New Cardanol Derivatives through Combined Iodination/Palladium-Catalysed Cross-Coupling Reactions

Antonio Arcadi*a, Orazio. A. Attanasib, Stefano Berrettab, Gabriele Bianchia, Paolino Filipponeb
a Dipartimento di Chimica, Ingegneria Chimica e Materiali, Università dell’Aquila, via Vetoio, 67100 L’Aquila, Italy
b Centro di Studio delle Sostanze Organiche di Orgine Naturale, Università di Urbino, Via Sasso 75, 61029 Urbino, Italy
Fax: +39(0862)433753.; e-Mail: arcadi@univaq.it;
Further Information

Publication History

Received 10 March 2006
Publication Date:
26 June 2006 (online)

Abstract

A versatile approach to the synthesis of new cardanol derivatives through a combination of aromatic iodination of 3-n-pentadecylphenol and palladium-catalysed cross-coupling reactions has been developed. The extent of aromatic iodination is controlled by stoichiometry and affords either the mono-, di- or tri-iodo-cardanol derivatives. Suzuki, Heck and Sonogashira protocols were successfully applied for the vinylation, arylation and alkynylation of the iodo-cardanols. 2,4-Diiodo-5-n-pentadecylphenol underwent an unusual sequential regioselective dehalogenation/vinylation reaction. Sequential alkynylation/cyclisation of 2-iodo-3-n-pentadecylphenol derivatives were also investigated.

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18

The antioxidant properties of 3a,c were determined by kinetic measurements (inhibition rate constants Kinh M-1s-1); The inhibition rate constants for 3a,c are 6.2 × 10-3 M-1s-1 and 6.5 × 10-3 M-1s-1, respectively. For comparison, the inhibition rate constant of the commercial antioxidant 2,6-di-tert-butyl-4-methylphenol (BHT) is 2.6 × 10-4 M-1s-1.