SYNTHESIS OF THIOMETHYLATED CALIX[4]RESORCINARENE BASED ON FENNEL OIL VIA CHLOROMETHYLATION

Suryadi Budi Utomo (Chemical Education Study Program, PMIPA FKIP, Sebelas Maret University, Surakarta)
Jumina Jumina (Chemistry Department, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Yogyakarta)
Dwi Siswanta (Chemistry Department, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Yogyakarta)
Mustofa Mustofa (Department of Pharmacology and Toxicology, Faculty of Medicine, Universitas Gadjah Mada, Yogyakarta)
Naresh Kumar (School of Chemistry, Faculty of Science, University of New South Wales, Sydney, NSW 2052)

Indonesian Journal of Chemistry
Vol 11, No 1 (2011)

A research has been conducted to synthesize thiomethylated-C-4-methoxyphenylcalix[4]resorcinarene using fennel oil as a starting material. The synthesis was carried out in four steps i.e. (1) oxidation of anethole to yield p-anisaldehyde, (2) HCl-catalyzed condensation of p-anisaldehyde with resorcinol, (3) chloromethylation of C-4-methoxyphenylcalix[4]resorcinarene with paraformaldehyde and HCl in the presence of ZnCl2 to yield tetrakis-chloromethyl-C-4-methoxyphenylcalix[4]resorcinarene, and (4) reaction of tetrakis-chloromethyl-C-4-methoxyphenylcalix[4]resorcinarene with thiourea followed by hydrolysis with sodium hydroxide solution to yield tetrakis-thiomethyl-C-4-methoxyphenylcalix[4]resorcinarene. The prepared compounds were characterized based on melting point, FT-IR, and NMR spectrometers. According to the analysis of 1H-NMR spectrometer, C-4-methoxyphenylcalix[4]resorcinarene and tetrakis-chloromethyl-C-4-methoxyphenylcalix[4]resorcinarene were observed in the chair or flattened partial cone conformation, while tetrakis-thiomethyl-C-4-methoxyphenylcalix[4]resorcinarene tend to exist in the crown or cone conformation.