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Terpenoids from Steyermarkina dispalata (Asteraceae)
Biochemical Systematics and Ecology 26 (1998) 453 — 455
Terpenoids from Steyermarkina dispalata (Asteraceae) Denise Aparecida Soares Massei, Dione´ia Camilo, Rodrigues de Oliveira, Joa8 o Luis Callegari Lopes* Departamento de Fı& sica e Quı& mica, Faculdade de CieL ncias FarmaceL uticas de RibeiraJ o Preto, Universidade de SaJ o Paulo, Via do Cafe& s/n, 14040-903, RibeiraJ o Preto, S.P., Brazil Received 29 August 1997; accepted 20 November 1997 Keywords: Steyermarkina dispalata; Eupatorieae; Asteraceae; Diterpenes; Kauranes; Triterpenes
1. Subject and source The genus Eupatorium L. was subject of a reclassification by King and Robinson between 1966 and 1986 into numerous smaller genera (King and Robinson, 1987). One of these is Steyermarkina King and Robinson, included in the sub-tribe Critoniinae, with four recognized species: three Brazilian (S. dispalata (Gardner) King and Robinson, S. dusenii (Malme) King and Robinson and S. pyrifolia (DC.) King and Robinson) and one Venezuelan S. triflora King and Robinson. The Brazilian species were previously included as Eupatorium sensu lato by Cabrera and Vittet (1963). As part of our phytochemical studies on members of the Eupatorieae we report here the terpenoids content of S. dispalata. The plant was collected by Lopes in Morro de Santa Rosa´lia, in Poios de Caldas, Minas Gerais, Brazil, in December 1984 and identified by the late Dr. Hermo´genes de Freitas Leita8 o Filho; a voucher specimen (Collection Number — Lopes 146) has been deposited in the Herbarium of the Instituto de Biologia, Universidade Estadual de Campinas, S.P., Brazil.
*Corresponding author. This article is dedicated to the late Professor Hermo´genes F. Leita8 o Filho 0305-1978/98/$19.00 ( 1998 Elsevier Science Ltd. All rights reserved. PII: S 03 0 5-1 9 78 ( 9 7) 0 0 13 5 - X
454
D.A.S. Massei et al./Biochemical Systematics and Ecology 26 (1998) 453—455
2. Previous work From the chemical point of view nothing has been reported on the genus Steyermarkina or on Eupatorium dispalatum Gardner (syn.).
3. Present study Dried and pulverized aerial parts of S. dispalata (3.7 kg) were sequentially extracted at room temperature with hexane : EtOAc (8 : 2) and EtOH to give 79.2 g and 43.8 g of crude extract. The crude hexane : EtOAc (8 : 2) extract was dissolved in MeOH: H O 2 (9 : 1) and extracted with hexane and then with CH Cl . 2 2 The hexane phase was concentrated under reduced pressure and chromatographed on a column of Si gel, eluting with hexane followed by mixtures of hexane—EtOAc of increasing polarity and finally MeOH. Seventy fractions of 150 ml were collected, monitored and combined on the bases of TLC analysis. The fractions eluted with hexane—EtOAc 19 : 1 (4.3 g) on rechromatography over Si gel (CC) with mixtures of hexane : EtOAc of increasing polarity furnished friedelin (1) (0.3 g), 1.1 g of ent-kaur16-en-19-oic acid (2) and 0.1 g of ent-kauran-16b-ol (3). The concentrate and dried CH Cl phase (7.1 g) was chromatographed over Si gel 2 2 (CC) eluting with hexane followed by mixtures of hexane—EtOAc of increasing polarity and finally MeOH. Two-hundred twenty eight fractions of 100 ml each were collected, monitored and combined on the basis of TLC analysis. The fractions eluted with hexane—EtOAc 4 : 1 (1.1 g) on rechromatography over Si gel (CC) afforded 0.3 g of ent-15a-hydroxykaur-16-en-19-oic acid (4) and 0.2 g of 2. The fractions eluted with hexane—EtOAc 1 : 1 (0.5 g) on PTLC (Si gel, hexane—EtOAc 7 : 3) gave a mixture 1 : 1 of the two triterpenes friedelan-3b-ol (5) and 1. The crude ethanolic extract (21.6 g) was chromatographed through the same procedure and 170 fractions of 130 ml each were collected. The fractions eluted with hexane—EtOAc 4 : 1 (1.2 g) on recrystallization (MeOH) gave 2 (0.9 g). The fractions eluted with hexane—EtOAc 7 : 3 (0.4 g) on rechromatography using chromatotron (Si gel, Hexane—EtOAc 8 : 2) afforded 0.07 g of ent-15b-tiglyloxykaur16-en-19-oic acid (6) and 0.03 g of ent-15b-angeloxykaur-16-en-19-oic acid (7). Finally, the fractions eluted with hexane—EtOAc 1 : 1 (0.29 g) and 3 : 7 (0.70 g) afforded on PTLC (Si gel, hexane-EtOAC 1 : 1) 0.40 g of 4 and 0.30 g of ent-17-hydroxykaur-15en-19-oic acid (8). The structures of the known diterpenes were confirmed by comparison of their NMR spectral data with those reported in the literature: 2 (Ohno et al., 1979), 3 (Brieskorn et al., 1969), 4 (Ekong et al., 1968; Hanson et al., 1976), 6 (Tomassini et al., 1979), 7 (Bohlmann et al., 1977; Gao et al., 1984) and 8 (Yahara et al., 1974; Ali et al., 1974). The identities of triterpenes 1 and 5 were confirmed by comparing their NMR spectral data with those reported (Werhrli et al., 1976; Wenkert et al., 1978; Gunatilaka et al., 1983) and GLC analysis using authentic samples.
D.A.S. Massei et al./Biochemical Systematics and Ecology 26 (1998) 453—455
455
4. Chemotaxonomic significance Diterpenes and triterpenes have been reported from many Eupatorieae, but entkaurane derivatives seem particularly common in Mikania (Dominguez, 1977; Bohlmann et al., 1981, 1982). Pyrrolizidine alkaloids and sesquiterpene lactones, common constituents of Eupatorium species, were not detected. The absence of these two classes of compounds might have some chemosystematic interest, because it is in agreement with the reclassification of King and Robinson. Further work will be needed to investigate the other secondary metabolites.
Acknowledgements We wish to thank Prof. Dr. Gil Valdo Jose´ da Silva for the NMR spectra and the late Prof. Dr. Hermo´genes de Freitas Leita8 o Filho for the plant identification. This work was supported by FAPESP, CNPq and CAPES.
References Ali, E., Dastidar, P.P.G., Pakrashi, S.C., 1974. J. Indian Chem. Soc. 51, 409. Bohlmann, F., Le Van, N., 1977. Phytochemistry 16, 579. Bohlmann, F., Adler, A., Schuster, A., Gupta, R.K., King, R.M., Robinson, H., 1981. Phytochemistry 20, 1899. Bohlmann, F., Singh, P., Jakupovic, J., Robinson, H., King, R.M., 1982. Phytochemistry 21, 705. Brieskorn, C.H., Poehlmann, E., 1969. Chem. Ber. 102, 2621. Cabrera, A.L., Vittet, N., 1963. Sellowia 15, 149. Dominguez, X.A., 1977. In: The Biology and Chemistry of the Compositae, (Heywood, V.H., Harborne, J.B., Turner, B.L., (Eds.), Academic Press, New York, p. 487. Ekong, D.E.U., Ogan, A.U., 1968. J. Chem. Soc. C 311. Gao, F., Miski, M., Gage, D.A., Mabry, T.J., 1984. J. Nat. Prod. 48, 316. Gunatilaka, A.A.L., Nanayakkara, N.P.D., Wazeer, M.I.M. 1983. Phytochemistry 22, 991. Hanson, J.R., Siverns, M., Piozzi, F., Savona, G., 1976. J. Chem. Soc. Perkin I, 114. King, R.M., Robinson, H., 1987. The Genera of the Eupatorieae (Asteraceae), Monographs in Systematic Botany from the Missouri Botanical Garden 22, 289. Ohno, N., Mabry, T.J., Zabel, V., Watson, W.H., 1979. Phytochemistry 18, 1687. Tomassini, T.C.B., Matos, M.E.O., 1979. Phytochemistry 18, 663. Wehrli, F.W., Nishida, T., 1976. Fortschritte d. Chem. Org. Naturst. 36, 24. Wenkert, R., Baddeley, G.V., Burfitt, I.R., Moreno, L.N., 1978. Org. Mag. Res. 11, 337. Yahara, S., Ishida, M., Yamasaki, K., Tanaka, O., Mihashi, S., 1974. Chem. Pharm. Bull. 22, 1629.
Terpenoids from Steyermarkina dispalata (Asteraceae) Denise Aparecida Soares Massei, Dione´ia Camilo, Rodrigues de Oliveira, Joa8 o Luis Callegari Lopes* Departamento de Fı& sica e Quı& mica, Faculdade de CieL ncias FarmaceL uticas de RibeiraJ o Preto, Universidade de SaJ o Paulo, Via do Cafe& s/n, 14040-903, RibeiraJ o Preto, S.P., Brazil Received 29 August 1997; accepted 20 November 1997 Keywords: Steyermarkina dispalata; Eupatorieae; Asteraceae; Diterpenes; Kauranes; Triterpenes
1. Subject and source The genus Eupatorium L. was subject of a reclassification by King and Robinson between 1966 and 1986 into numerous smaller genera (King and Robinson, 1987). One of these is Steyermarkina King and Robinson, included in the sub-tribe Critoniinae, with four recognized species: three Brazilian (S. dispalata (Gardner) King and Robinson, S. dusenii (Malme) King and Robinson and S. pyrifolia (DC.) King and Robinson) and one Venezuelan S. triflora King and Robinson. The Brazilian species were previously included as Eupatorium sensu lato by Cabrera and Vittet (1963). As part of our phytochemical studies on members of the Eupatorieae we report here the terpenoids content of S. dispalata. The plant was collected by Lopes in Morro de Santa Rosa´lia, in Poios de Caldas, Minas Gerais, Brazil, in December 1984 and identified by the late Dr. Hermo´genes de Freitas Leita8 o Filho; a voucher specimen (Collection Number — Lopes 146) has been deposited in the Herbarium of the Instituto de Biologia, Universidade Estadual de Campinas, S.P., Brazil.
*Corresponding author. This article is dedicated to the late Professor Hermo´genes F. Leita8 o Filho 0305-1978/98/$19.00 ( 1998 Elsevier Science Ltd. All rights reserved. PII: S 03 0 5-1 9 78 ( 9 7) 0 0 13 5 - X
454
D.A.S. Massei et al./Biochemical Systematics and Ecology 26 (1998) 453—455
2. Previous work From the chemical point of view nothing has been reported on the genus Steyermarkina or on Eupatorium dispalatum Gardner (syn.).
3. Present study Dried and pulverized aerial parts of S. dispalata (3.7 kg) were sequentially extracted at room temperature with hexane : EtOAc (8 : 2) and EtOH to give 79.2 g and 43.8 g of crude extract. The crude hexane : EtOAc (8 : 2) extract was dissolved in MeOH: H O 2 (9 : 1) and extracted with hexane and then with CH Cl . 2 2 The hexane phase was concentrated under reduced pressure and chromatographed on a column of Si gel, eluting with hexane followed by mixtures of hexane—EtOAc of increasing polarity and finally MeOH. Seventy fractions of 150 ml were collected, monitored and combined on the bases of TLC analysis. The fractions eluted with hexane—EtOAc 19 : 1 (4.3 g) on rechromatography over Si gel (CC) with mixtures of hexane : EtOAc of increasing polarity furnished friedelin (1) (0.3 g), 1.1 g of ent-kaur16-en-19-oic acid (2) and 0.1 g of ent-kauran-16b-ol (3). The concentrate and dried CH Cl phase (7.1 g) was chromatographed over Si gel 2 2 (CC) eluting with hexane followed by mixtures of hexane—EtOAc of increasing polarity and finally MeOH. Two-hundred twenty eight fractions of 100 ml each were collected, monitored and combined on the basis of TLC analysis. The fractions eluted with hexane—EtOAc 4 : 1 (1.1 g) on rechromatography over Si gel (CC) afforded 0.3 g of ent-15a-hydroxykaur-16-en-19-oic acid (4) and 0.2 g of 2. The fractions eluted with hexane—EtOAc 1 : 1 (0.5 g) on PTLC (Si gel, hexane—EtOAc 7 : 3) gave a mixture 1 : 1 of the two triterpenes friedelan-3b-ol (5) and 1. The crude ethanolic extract (21.6 g) was chromatographed through the same procedure and 170 fractions of 130 ml each were collected. The fractions eluted with hexane—EtOAc 4 : 1 (1.2 g) on recrystallization (MeOH) gave 2 (0.9 g). The fractions eluted with hexane—EtOAc 7 : 3 (0.4 g) on rechromatography using chromatotron (Si gel, Hexane—EtOAc 8 : 2) afforded 0.07 g of ent-15b-tiglyloxykaur16-en-19-oic acid (6) and 0.03 g of ent-15b-angeloxykaur-16-en-19-oic acid (7). Finally, the fractions eluted with hexane—EtOAc 1 : 1 (0.29 g) and 3 : 7 (0.70 g) afforded on PTLC (Si gel, hexane-EtOAC 1 : 1) 0.40 g of 4 and 0.30 g of ent-17-hydroxykaur-15en-19-oic acid (8). The structures of the known diterpenes were confirmed by comparison of their NMR spectral data with those reported in the literature: 2 (Ohno et al., 1979), 3 (Brieskorn et al., 1969), 4 (Ekong et al., 1968; Hanson et al., 1976), 6 (Tomassini et al., 1979), 7 (Bohlmann et al., 1977; Gao et al., 1984) and 8 (Yahara et al., 1974; Ali et al., 1974). The identities of triterpenes 1 and 5 were confirmed by comparing their NMR spectral data with those reported (Werhrli et al., 1976; Wenkert et al., 1978; Gunatilaka et al., 1983) and GLC analysis using authentic samples.
D.A.S. Massei et al./Biochemical Systematics and Ecology 26 (1998) 453—455
455
4. Chemotaxonomic significance Diterpenes and triterpenes have been reported from many Eupatorieae, but entkaurane derivatives seem particularly common in Mikania (Dominguez, 1977; Bohlmann et al., 1981, 1982). Pyrrolizidine alkaloids and sesquiterpene lactones, common constituents of Eupatorium species, were not detected. The absence of these two classes of compounds might have some chemosystematic interest, because it is in agreement with the reclassification of King and Robinson. Further work will be needed to investigate the other secondary metabolites.
Acknowledgements We wish to thank Prof. Dr. Gil Valdo Jose´ da Silva for the NMR spectra and the late Prof. Dr. Hermo´genes de Freitas Leita8 o Filho for the plant identification. This work was supported by FAPESP, CNPq and CAPES.
References Ali, E., Dastidar, P.P.G., Pakrashi, S.C., 1974. J. Indian Chem. Soc. 51, 409. Bohlmann, F., Le Van, N., 1977. Phytochemistry 16, 579. Bohlmann, F., Adler, A., Schuster, A., Gupta, R.K., King, R.M., Robinson, H., 1981. Phytochemistry 20, 1899. Bohlmann, F., Singh, P., Jakupovic, J., Robinson, H., King, R.M., 1982. Phytochemistry 21, 705. Brieskorn, C.H., Poehlmann, E., 1969. Chem. Ber. 102, 2621. Cabrera, A.L., Vittet, N., 1963. Sellowia 15, 149. Dominguez, X.A., 1977. In: The Biology and Chemistry of the Compositae, (Heywood, V.H., Harborne, J.B., Turner, B.L., (Eds.), Academic Press, New York, p. 487. Ekong, D.E.U., Ogan, A.U., 1968. J. Chem. Soc. C 311. Gao, F., Miski, M., Gage, D.A., Mabry, T.J., 1984. J. Nat. Prod. 48, 316. Gunatilaka, A.A.L., Nanayakkara, N.P.D., Wazeer, M.I.M. 1983. Phytochemistry 22, 991. Hanson, J.R., Siverns, M., Piozzi, F., Savona, G., 1976. J. Chem. Soc. Perkin I, 114. King, R.M., Robinson, H., 1987. The Genera of the Eupatorieae (Asteraceae), Monographs in Systematic Botany from the Missouri Botanical Garden 22, 289. Ohno, N., Mabry, T.J., Zabel, V., Watson, W.H., 1979. Phytochemistry 18, 1687. Tomassini, T.C.B., Matos, M.E.O., 1979. Phytochemistry 18, 663. Wehrli, F.W., Nishida, T., 1976. Fortschritte d. Chem. Org. Naturst. 36, 24. Wenkert, R., Baddeley, G.V., Burfitt, I.R., Moreno, L.N., 1978. Org. Mag. Res. 11, 337. Yahara, S., Ishida, M., Yamasaki, K., Tanaka, O., Mihashi, S., 1974. Chem. Pharm. Bull. 22, 1629.