Biochemical Systematics and Ecology 33 (2005) 555–558 www.elsevier.com/locate/biochemsyseco

Quinoline alkaloids from corniculata ()

Daniela de Nazare´M. Machadoa, Sebastia˜ o F. Palmeira Ju´niora, Lucia M. Conservaa,*, Rosangela P. de Lyra Lemosb

aDepartamento de Quı´mica, Universidade Federal de Alagoas, 57072-970 Maceio´, AL, Brazil bInstituto do Meio Ambiente do Estado de Alagoas, 57017-320 Maceio´, AL, Brazil

Received 18 November 2003; accepted 20 August 2004

Keywords: Sebastiania corniculata; Euphorbiaceae; Hipomaneae; Quinoline alkaloids

1. Subject and source

Sebastiania corniculata (Vahl) Muell. Arg., is a perennial herb distributed in tropical America, including some regions of Brazil (Carneiro et al., 2002). The material was collected in A´rea de Protec¸a˜ o Ambiental de Santa Rita (Mucuri), Marechal Deodoro, Alagoas, Brazil, in November 1999 and identified by Rosangela P. de Lyra Lemos of the Departamento de Botaˆ nica do Instituto do Meio Ambiente do Estado de Alagoas (IMA/AL), where a voucher specimen was deposited (MAC- 10763).

* Corresponding author. Tel.: C55 82 214 1384; fax: C55 82 214 1615. E-mail address: [email protected] (L.M. Conserva).

0305-1978/$ - see front matter Ó 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.bse.2004.08.004 556 D.deN.M. Machado et al. / Biochemical Systematics and Ecology 33 (2005) 555–558

2. Previous work

Previous phytochemical studies on Sebastiania reported the occurrence of acetophenone (xanthoxylin) from aerial parts of Muell. Arg. (Calixto et al., 1990; Yunes et al., 1990), flavonoids (quercetin, kaempferol, quercitrin) and other phenolic derivatives (gallic acid, methylgallate and proto- catechuic acid) from leaves of Spreng. (Penna et al., 2001), terpenoids (glutinol, a- and b-amyrin, moretenone, campesterol, stigmasterol and b- sitosterol) from aerial parts and roots of S. schottiana Muell. Arg. (Yunes et al., 1990; Gaertner et al., 1999; Branco and Pizzolatti, 2002). Hydrocarbons, carboxylic acids, methyl esters and triterpenes (lupeol, glutinol, a- and b-amyrin, olean-13(18)- en-3-ol, moretenone) were also identified by HRGC–MS from aerial parts of Sebastiania argutidens Pax & Hoffm. (Branco and Pizzolatti, 2002).

3. Present study

The air-dried and powdered material from the whole plant of S. corniculata (1360 g) was extracted with acetone and 90% EtOH at room temperature. The crude acetone extract (38 g) was suspended in MeOH/H2O (3:2) solution and extracted successively with C6H14 and CH2Cl2. The C6H14 residue (14.6 g) was monitored by TLC and resuspended in aq. NaOH 4% and extracted with C6H14. Neutral fraction (13.8 g) was chromatographed on silica gel column with C6H14 containing increasing amounts of EtOAc. The A (0.56 g) and B (0.53 g) fractions, after gel permeation on Sephadex LH-20 (MeOH) and successive recrystallizations from MeOH, afforded sitostenone (29 mg) and a mixture of sitosterol and stigmasterol (92 mg). The remaining fractions (C, 0.43 g and D, 0.23 g) were submitted to gel permeation (Sephadex LH-20 from MeOH) and preparative TLC (silica gel PF254 and C6H6/ EtOAc (3:1)) to afford 1 (11 mg) and a mixture containing 2–3 (34 mg). Structures of all isolated compounds were identified on the basis of their spectral data (IR, NMR, MS, including DEPT, COSY, HMQC and HMBC experiments) and by comparison of their spectral data with values in the literature. Compounds 1 and 2 were identified as 3,4,8-trimethoxy-2-quinolone (Sarker et al., 1995) and 2,3-methylenedioxy-4,7,8- trimethoxyquinoline (Cha´vez et al., 1997), respectively. Compound 3, to best of our knowledge, has not been previously reported and its structure was elucidated by its spectral data and by comparison with compound 2 (Cha´vez et al., 1997) and with 2,3- methylenedioxy-4,7-dimethoxyquinoline (Cui et al., 1999).

OMe

OMe

N O

OMe H

1 D.deN.M. Machado et al. / Biochemical Systematics and Ecology 33 (2005) 555–558 557

OMe

O

O R1 N

R2

2 R1 = R2 = OMe

3 R1 = H, R2 = OMe

2,3-Methylenedioxy-4,8-dimethoxyquinoline (3). Oil. IR (KBr, cmÿ1): 2923, 2850, 1 1615, 1540, 1360, 1267, 1106, 1052, 748; H NMR (CDCl3, 300 MHz) d 6.92 (dd, J Z 8; 2.1, H-7), 7.26 (t, J Z 8, H-6), 7.55 (dd, J Z 8; 2.1, H-5), 6.03 13 (s, OCH2O), 4.26 (s, MeO-4), 3.98 (s, MeO-8); C NMR (CDCl3, 75 MHz) d 159.1 (C-2), 123.8 (C-3), 142.0 (C-4), 113.6 (C-5), 124.3 (C-6), 107.6 (C-7), 154.2 (C-8), 134.1 (C-9), 122.5 (C-10), 99.3 (OCH2O), 59.5 (MeO-4), 55.9 (MeO-8); HMQC correlations: [d 6.03 (99.3), 6.92 (107.6), 7.26 (124.3), 7.55 (113.6), 4.26 (59.5), 3.98 (55.9)]; main HMBC correlations: [OCH2O (C-2 and C-3), MeO-4 (C- 4), H-5 (C-4, C-6 and C-10), H-6 (C-5, C-7, C-8 and C-9), H-7 (C-5, C-8 and C-10), MeO-8 (C-8)].

4. Chemotaxonomic significance

According to Webster (1994) the family Euphorbiaceae comprises about 317 genera, distributed in 49 tribes and five subfamilies. Several structural types of alkaloids useful for chemosystematic purposes have previously been reported in the different tribes of this family (Ritz, 1987; Seigler, 1994). In the tribe Hipomaneae, which contains the genus Sebastiania, only piperidine and indole alkaloids have been so far reported (Ritz, 1987; Seigler, 1994). So, this is the first time that this structural type of alkaloid has been found in the genus Sebastiania, and to our knowledge, no quinoline alkaloid has been found in this tribe.

Acknowledgements

This work was supported by Conselho Nacional de Desenvolvimento Cientı´fico e Tecnolo´gico (CNPq), Instituto do Mileˆ nio do Semi-A´rido (IMSEAR), and Fundac¸a˜ o de Amparo a` Pesquisa do Estado de Alagoas (FAPEAL). The authors are grateful to Dr. Edilberto Rocha Silveira, Centro Nordestino de Aplicac¸a˜ oe Uso de RMN da Universidade Federal do Ceara´(CENAUREN) for the NMR spectra. 558 D.deN.M. Machado et al. / Biochemical Systematics and Ecology 33 (2005) 555–558

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