1598 zyxwvutsrqponmlkjihgfedcbaZYXWVUTSRQPONMLKJIHGFEDCBA Journal of Natural Pmdvcts Val. 56, No. 9, pp. 1598-1600, zyx A September 1993 zyxwvuts BIOACTIVE METABOLITES FROM SICILIAN MARINE FENNEL, CRITHMUM MARITIMUM FRANCESCA CLJNSOLO, zyxw GFED GILISEPPE RLEIERTO,* Istituto zyxwvuts del C. N.R. per lo Studio delle Sostanze Natural; di Interesse Alimentae e C h i m i c a - F , Via del Santuario, I IO 1-95028 Valwde (CT), Italy VINCENZO AMICO, and zyxw FEDC WO FIATIFLLI Dipattimento di Scienze Chimube dell'llniwsitrj di Catania, V.le A. D&, 6 1-95125 Catania, Italy hmcr.-Bioactivity-guided fractionation of the lipid extract of Crithmum muritimrtm using the brine shrimp lethality assay led to the isolation of three bioactive compounds. Two of these zyxwvut are known zyxwvu FEDCBA C,, polyacetylenic metabolites, falcarinol {I] and falcarindiol (21, previously isolated from several species of the Umbelliferae and Araliaceae. The third active prin identified as 0-geranylvanillin [33, an aromatic ether described in the literature as a synthetic compound but unknown as a natural product. Cytotoxic activity of the pure compounds was significant for 1 and 2, much less intense for 3. Crithmum muritimum L. (Umbelli- ferae), popularly known as marine fennel, is a shrub which grows on maritime rocks, piers, and breakwaters, more rarely on sandy beaches along the European coasts (1,2). The whole plant is eaten raw for its tonic and depurative qualities, while an infusion of leaves reputedly aids digestive and diuretic activities (3). Ow- ing to the antiscorbutic property, in times past sailors used to consume food prepa- rations based on leaves of C. maritimum to prevent scuny(4). For its particular taste, marine fennel is also used locally as a substitute for capers ( 5 ) . Since present phytochemical knowledge of this plant is scant (GlO), in the course of a program aimed at the identification of bioactive constituents of plants of the Sicilian flora we have examined the lipid extract of C. maritimum and here we report the results of this investigation. Si gel chromatography of the CH2C12 extract of the freeze-dried leaves of C. muritimum gave several fractions active in the Artemia salina assay, which is known to give information on cytotoxic and in- secticidal properties. Further purification by preparative layer chromatography (plc) of the main bioactive fractions yielded three pure compounds, 1-3. Two of these were easily identified as falcarinol117 (also known as panaxynol) OH 1 R=H 2 R=OH and falcarindiol 127, originally isolated, respectively, from Panax ginseng C.A. Meyer (1 1) and Falcaria vulgaris Bernh. (1 2 ) , and subsequently identified in many species of the Umbelliferae (13,14) and Araliaceae (1 5 ) . The third bioactive me- tabolite was an optically inactive oil, C18H2403 (hreims). Its ir spectrum con- tained an intense carbonyl absorption, while the uv spectrum showed bands indicative of an aromatic chromophore. The 'H-nmr spectrum displayed reso- nances for three aromatic protons whose coupling allowed us to deduce the substi- tution pattern on the benzene ring, as well as a formyl and a methoxyl group. The third substituent was identified as a linear monoterpene chain bound to the aromatic nucleus through an oxygen atom. Assignments and couplings were deduced