The aromaticity of some of these rings was evident by the characteristic downfield shifts observed for five methine resonances in the 1H NMR spectrum (H 9.21, 8.07, 7.51, 7.50, and 6.94). Table 2 1H NMR Spectroscopic Data (500 MHz, in Hz)) for Compounds 6-8 in MeOH-(H 1.92) and H-20/4established the -orientation of these protons. Kupchan partitioning scheme to yield hexane, EtOAc, and 367.1540 [M + H]+ in the HRMS data indicating a molecular formula of C22H22O5 and 12 double bond equivalents. The IR spectrum of xestosaprol F (1) showed strong absorptions for hydroxy (3382 cm-1) and ,-unsaturated ketone moieties (1649 cmC1). The presence of this latter functional group was also supported by the resonance observed at 178.4 ppm in the 13C NMR spectrum. Further analyses of the 13C (Table 2) and multiplicity-edited HSQC NMR spectra showed the 22 carbon resonances could be ascribed to five methylenes, seven methines, and nine quaternary carbons, in addition to a Voreloxin Hydrochloride single methyl group. On the basis of chemical shift considerations, 12 of these carbons, in addition to the carbonyl resonance, were sp2 hybridized indicating 1 contained six carbon-carbon double bonds and five rings. The aromaticity of some of these rings was evident by the characteristic downfield shifts observed for five methine resonances in the 1H NMR spectrum (H 9.21, 8.07, 7.51, 7.50, and 6.94). Table 2 1H NMR Spectroscopic Data (500 MHz, in Hz)) for Compounds 6-8 in MeOH-(H 1.92) and H-20/4established the -orientation of these protons. As the magnitude of the coupling constants observed within this ring were consistent with a chair conformer, the series of small couplings evident for H-3 established an equatorial position on Voreloxin Hydrochloride the -face of the molecule. These observations are consistent with the broad singlet observed for the equatorial proton at C-3 in the previously reported xestosaprol A as well.3 Compound 2 was obtained as a yellow powder. Comparison of the NMR spectra of 2 (Tables 1 and ?and2)2) with those of 1 1 revealed that 2 possessed a similar structure, except for the absence of the resonances corresponding to the ethylene glycol residue observed in 1. Analysis of the HRMS data for 2 yielded a molecular formula of C20H18O4 that was C2H4O smaller than that observed for 1. Analysis of the 13C NMR and DEPT spectra confirmed the loss of this unit and the formation of the corresponding phenolic compound. Therefore, 2 was assigned the trivial name xestosaprol G. Table 1 1H NMR Spectroscopic Data (500 MHz, Voreloxin Hydrochloride in Hz)) for Compounds 1-5 (MeOH-(Order Haplosclerida: Family Petrosiidae), that has been referred to previously as (Duchassaing et Michelotti, 1864) by Desqueyroux-Faundez (1987) for New Caledonian specimens. The species name is currently considered to be invalid and restricted to sponges in the western central Atlantic, from where the species was first described. Voucher specimens have been deposited in the Natural History Museum, London (BMNH 2009.8.12.1-2). Extraction and Isolation The freeze-dried sponge (93 g) was chopped Voreloxin Hydrochloride into small pieces and then exhaustively extracted with MeOH (5 1 L) at room temperature to afford 6.0 g of lipophilic extract. The residue was suspended in H2O and partitioned with hexane, EtOAc and 0.2, MeOH); UV (MeOH) max (log ) 221 (4.2), 249 (3.8), 271 Rabbit Polyclonal to Ik3-2 (3.8), 332 (3.4), 379 (3.4) nm; IR (CaF2) max 3382, 1649, 1619 cm-1; See Tables 1 and ?and22 for NMR spectroscopic data; HRESI-TOFMS 367.1540 [M + H]+ (calcd for C22H23O5+, 367.1546; = -1.5 ppm). Xestosaprol G (2): yellow powder; []D22 -8.7 (0.2, MeOH); UV (MeOH) max (log ) 224 (3.5), 271 (3.3), 335 (3.2), 364 (3.3) nm; IR (CaF2) max 3396, 1650, 1316 cm-1; See Tables 1 and ?and22 for NMR spectroscopic data; HRESI-TOFMS 323.1279 [M + H]+ (calcd for C20H19O4+, 323.1283; = -1.4 ppm). Xestosaprol H (3): yellow powder; []D22 -10 (0.2, MeOH); UV (MeOH) max (log ) 223 (3.7), 246 (3.4), 269 (3.4), 330 (3.0), 382 (2.8) nm; IR (CaF2) max 3417, 1650 cm-1; See Tables 1 and ?and22 for NMR spectroscopic data; HRESI-TOFMS 367.1540 [M + Voreloxin Hydrochloride H]+ (calcd for C22H23O5+, 367.1546; = -1.5 ppm). Xestosaprol I (4): yellow powder; []D22 -27 (0.2, MeOH); UV (MeOH) max (log ) 217 (3.9), 242 (3.7), 264 (3.6), 325 (3.3) nm; IR (CaF2) max 3411, 1655 cm-1; See Table 1 for NMR spectroscopic data; HRESI-TOFMS 307.1326 [M + H]+ (calcd for C20H19O3+, 307.1334; = -2.7 ppm). Xestosaprol J (5): yellow powder; []D22 -42 (0.2, MeOH); UV (MeOH) max (log ) 220 (4.0), 270 (3.7), 332 (3.3) nm; IR (CaF2) max 3417, 1650 cm-1; See Tables 1 and ?and22 for NMR spectroscopic data; HRESI-TOFMS 337.1434 [M + H]+ (calcd for C21H21O4+ , 337.1440; = -1.7 ppm). Xestosaprol K (6): yellow powder; []D22.