Three highly functionalized pyrroloquinoline alkaloids, batzelline A (l), B (2), and C (3) were isolated from the deep water Bahamas sponge Batzella sp. The structure of 1 was determined by X-ray and those of 2 and 3 deduced by comparison of their spectral data with that of 1 and by chemical transformations.
In search of herbicidal agents from marine organisms, three nitrogenous pigments, batzellines A (l), B (2), and C (3) were found in the sponge Bafzelia sp. In view of their unusual nature, we now describe details of their isolation and the elucidation of their structures A sample was collected in July 1984 using the Johnson-Sea-Link submersible between Freeport and West End in the Grand Bahama Islands at a depth of 120 m. The frozen sponge (68 g) was repeatedly extracted with methanol-chloroform (21). The extract was concentrated in vacua to give an aqueous suspension which was further extracted with ethyl acetate. This last extract was fractionated on an Ito multi-layer coil planet centrifuge (CPC) with heptane-EtOAc-MeOH-HsO (4:7:4:3, lower phase stationary). The stationary phase was re-chromatographed on the CPC (heptane-EtOAc-MeOH-HsO, 2:7:6:3, lower phase stationary) to yield a pure compound, batzelline A (1, 107 mg), and a fraction containing two minor components. Subsequent countercurrent chromatography on CPC employing CHCla-iPr,NH-MeOH-HsO (7:1:6:4, lower phase stationary) afforded pure batzelline B (2, 26 mg) and C (3, 12 mg). All three compounds were obtained as dark brown solids, however 1 and 3 gave purple solutions and 2 a greenish yellow one. R' R2 x1 x2 Me H SMe Cl H H Shle Cl 3 MeH H Cl Me Me We Cl MeHH II Batzelline A (1) was recrystallized from CHCls-MeOH as black prisms, melting point 205'C. High resolution EIMS and "C NMR established the molecular formula as C,sH,,N,O,SCl.' Its methanolic solution displayed UV absorbance at 214 (t 8,900), 269 (E 22,100), 356 (E 7,900), 376 (E 8,000). and 548 nm (E 600) indicative of an aromatic molecule. The presence of an S-methyl, N-methyl, N-methylene, and an allylic methylene group including eight non-protonated sp2 carbon atoms in 1 was deduced from its 'H and "C NMR data (Table ).