Drimane-Type Sesquiterpenoids as Chemosystematic Markers of Canellaceae *

Capsicodendron dinisii was collected near Curitiba and identified by Dr. Gerdt Hatschbach (Herb. Museu Botânico Municipal, Curitiba). Dried, milled stem bark (2.5 kg) was extracted successively with C6H14 and EtOH. The solutions were filtered and evaporated to dryness, leading respectively to 61 and 250 g of extract. The C6H14-extract was partitioned between C6H14 and MeOH-H2O 19:1. Both solutions were evaporated to dryness, leading respectively to 18 and 38 g of residue. The latter partition fraction of the crude hexane extract was submitted to column chromatography (Si gel, 60 g). The following fractions were eluted with the indicated solvents: A (15 g, C6H14), B (11 g, CH2Cl2), C (7 g, AcOEt), D (4g, EtOH). Subsequent fractionation on column chromatography, preparative TLC (Si gel) and recrystallization led from A to 8 (23 mg), 2 (54 mg) and 1d (14 mg); and from C to 1d (800 mg), 1e (tetramer of 1d, 55 mg) and 1c (26 mg), in this order. 1d (1 g) was obtainde from B by cryst. from C6H14-Me2CO. The mother liquor was evaporated to dryness. The residue (10 g), submitted to column chromatography and preparative TLC (Si gel) gave 1a (83 mg). Poligonone (8), yellow crystals, mp 123-135° (C6H14). UV λmax MeOH nm: 237 (ε 7000). H NMR (60 MHz, CDCl3) δ: 0.90, 0.93, 1.30 ( s, 3Me), 1.32.1 (m, 7H), 2.3-2.6 (m, 2H-6), 6.30 (s, H-9), 9.60 (s, Article


Results and Discussion
During the present work a fresh sample of stem bark was collected from a tree in the vicinity of Curitiba, Paraná State.Fractionation of a hexane extract led to 1d and 1e, additionally to polygodial (1a), mukaadial (1c), isopolygodial (2) and polygonone (8).With the exception of 8 all other compounds have been found previously in other species of the family Canellaceae (Table 1).In each case the identification, achieved by analysis of UV, IR, 1 H NMR, 13 C NMR and mass spectra, was confirmed by comparison of mp, specific rotation and with published data.
The nor-sesquiterpene polygonone (8) was mentioned previously twice in the literature.First as the oxidation product of polygonal, an isolate of Polygonum hydropiper (Polygonaceae 2 , and subsequently as an authentic constituent of this species 3 .Nevertheless published data on this compound are restricted to the registry of two 1 H-NMR (60 MHz, CDCl3) peaks (δ: 1.07, s, 9H; 10.36, s, CHO) and of some MS peaks (m/z: 220, 215, 192, 124, 109) 3 .For this reason more data are given in the Experimental of the present communication.
In addition to Canellaceae and Polygonaceae, Porellaceae 3  aceae both belong to the superorder Magnoliiflorae, albeit to different orders, respectively Annonales and Magnoliales 5 .However, Porellaceae belong to the class Hepaticae of the division Bryophyta and Polygonaceae, although angiosperms show morphologically and chemically (presence of gallotannins and ellagitannins) no close kinship with the magnolialean families (absence of such tannins) 6 .
Nevertheless within the Canellaceae drimanic compounds constitute a neat unifying theme.True only one of such sesquiterpenoids (1d) has so far been isolated from all three genera, Capsicodendron, Warburgia and Cinnamosma, but four drimanes (1a, 1c, 2, 3b) are common to the first two genera, two (4a, 5a) are common to the last two genera, one (4c) is common to the first and third genera and only one again ( 7) is common to Warburgia and a fourth genus, Canella.Hence, considering identity of chemical composition, Capsicodendron and Warburgia show the closest relationship, followed by the pair Warburgia and Cinnamosma, with Capsicodendron and Cinnamosma as well as Warburgia and Canella still less closely retaled.Analogous trends are observed counting differences of compound composition.Both pairs, Capsicodendron and Warburgia as well as Warburgia and Cinnamosma, show ten differences, while the more distantly related Capsicodendron and Cinnamosma show 11 differences in drimane-type sesquiterpenoidal composition.From the morphological point of view the South American genera of Canellaceae are considered to be the most archaic 7 .Superposition of the chemical data on this postulate suggests a spacial radiation of the lineage to have taken place from tropical South American Capsicodendron in two directions, one towards the Caribbean Canella and the other over the tropical African Warburgia to the Madagascarian Cinnamosma.
The occurrence of shikimate derivatives, including a quaternary aporphine 8 , as replacement characters of drimane-type sesquiterpenoids in C. madagascariensis is consistent with the general placement of the family Canellaceae in the Magnoliiflorae.
in the last decade does not report the presence of this class of compounds in terrestrial plants, but in sponges 21,22 , in the fern Nephrolepsis biserrata 23 , in Polyporus articularis 24 and in the fungus Aspergillus ustus var.Pseudodeflectus 25 .