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Chemical constituents from Tillandsia recurvata
Fitoterapia 75 (2004) 423–425
Phytochemical communication
Chemical constituents from Tillandsia recurvata ´ de Queirogaa, Lucimara Mariano de Andradea, Marcos Aurelio a ˆ ´ Karina Chagas Florencio , Maria de Fatima Agraa, Marcelo Sobral da Silvaa, Jose´ Maria Barbosa-Filhoa, ˜ da-Cunhaa,b,* Emidio Vasconcelos Leitao a
´ ˆ ´ Laboratorio de Tecnologia Farmaceutica, Universidade Federal da Paraıba, Cx. Postal 5009, ˜ Pessoa, PB, Brazil 58051-970, Joao b ´ ´ Departamento de Farmacia e Biologia, Universidade Estadual da Paraıba, 58100-000, Campina Grande, PB, Brazil Received 12 May 2003; accepted 27 January 2004
Abstract The CHCl3 extract of Tillandsia recurvata yielded 5,39-dihydroxy-6,7,8,49-tetramethoxyflavanone (1), 1,3-di-O-cinnamoyl-glycerol (2) and ethyl ester of caffeic acid. Their structures were elucidated by means of spectroscopic methods such as mass spectroscopy and 1 and 2D-NMR. 䊚 2004 Elsevier B.V. All rights reserved. Keywords: Tillandsia recurvata; 5,39-Dihydroxy-6,7,8,49-tetramethoxyflavanone; 1,3-Di-O-cinnamoylglycerol
Plant. Tillandsia recurvata L. (Bromeliaceae), entire plant collected in September ´ 1999 near the City of Cabaceiras, State of Paraıba, Brazil, where it is popularly known as ‘barba de velho’ (old man’s beard) w1x. A voucher specimen (Agra 2190) is deposited in the Herbarium Prof. Lauro Pires Xavier (JPB) of the Universidade ´ Federal da Paraıba. *Corresponding author. Tel.yfax: q55-83-216-7364. E-mail address: [email protected] (E.V.L. da-Cunha). 0367-326X/04/$ - see front matter 䊚 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.fitote.2004.01.003
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M.A. de Queiroga et al. / Fitoterapia 75 (2004) 423–425
Uses in traditional medicine. No indications for this species. However, there are indications of medicinal uses of the species T. usneoides as hypoglycemic w2x, anti rheumatic and for liver infections w3x.
Previously isolated constituents. Triterpenoids w4x.
New-isolated constituents. 5,39-Dihydroxy-6,7,8,49-tetramethoxyflavanone (1) 52.0 mg, 1,3-di-O-cinnamoylglycerol (2) 48.5 mg and the ethyl ester of caffeic acid 58.6 mg from 655 g of the plant material.
5,39-Dihydroxy-6,7,8,49-tetramethoxyflavanone (1). Pale yellow oil; 1H-NMR (400-MHz, CDCl3): d 2.84 (1H, dd, J 3.1, 17.2 Hz, H-3 eq), 3.06 (1H, dd, J 12.6, 17.2 Hz, H-3 ax), 3.78 (3H, s, 8-OMe), 3.85 (3H, s, 7-OMe), 3.89 (3H, s, 49OMe), 4.07 (3H, s, 6-OMe), 5.33 (1H, dd, J 3.1, 12.6 Hz, H-2), 6.86 (1H, d, J 8.3 Hz, H-59), 6.92 (1H, dd, J 1.9, 8.3 Hz, H-69), 7.04 (1H, d, J 1.9 Hz, H-29), 11,76 (1H, s, 5-OH); 13C-NMR (100 MHz, CDCl3) d 43.7 (C-3), 56.2 (49-OMe), 61.3 (8-OMe), 61,6 (7-OMe), 61.7 (6-OMe), 79.2 (C-2), 104.4 (C-4a), 110.9 (C-59), 112.8 (C-29), 118,2 (C-69), 131.6 (C-19), 133.4 (C-8), 134.2 (C-6), 146.0 (C-39), 147.2 (C-49), 150.7 (C-8a), 152.0 (C-7), 155.7 (C-5), 197.4 (C-4); EI-MS myz: 376 wMxq (100), 360, 344. 1,3-Di-O-cinnamoylglycerol (2) White amorphous powder; 1H-NMR (400 MHz, CDCl3): d 4.27 (1H, quint, J 5.1 Hz, H-2), 4.36 (2H, dd, J 5.1, 11.6 Hz, H-1a and H-3a), 4.41 (2H, dd, J 5.1, 11.6 Hz, H-1b and H-3b), 6.49 (2H, d, J 16.0 Hz, H39 and H-30), 7.38 (6H, m, H-79, H-70, 89, 80, 99 and 90), 7.52 (4H, m, H-69, H-60, H-109 and H-100), 7.75 (2H, d, J 16.0 Hz, H-49 and H-40); 13C-NMR (100 MHz, CDCl3) d 65.7 (C-1 and C-3), 68.7 (C-2), 117.4 (C-39 and C-30), 128.4 (C-69, C60, C-109 and C-100), 129.1 (C-79, C-70, C-99 and C-90), 130.7 (C-89 and C-80), 134.4 (C-59 and C-50), 146.0 (C-49 and C-40), 167.2 (C-29 and C-20); EI-MS myz 353 wMqHxq, 335, 278, 223, 205 (100).
M.A. de Queiroga et al. / Fitoterapia 75 (2004) 423–425
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The 1H-NMR and 13C-NMR data for the two substances were assigned by means of one-dimensional and two-dimensional NMR techniques, such as COSY, NOESY, HETCOR and HMBC. Acknowledgments The authors wish to express their sincere thanks to CNPqyIMSEAR for financial support, to the NAPRALERT (SM) database of the University of Illinois-Chicago for the bibliographical information and to Dr A.I. Gray from the University of Strathclyde in Glasgow, Scotland for recording the NMR spectra. References w1x Correa ˆ MP. Dicionario ´ ´ ´ ´ ´ das plantas uteis do Brasil e das exoticas cultivadas. Brasılia: Ministerio da Agricultura, 1984. p. 265. w2x Witherup KM, McLaughlin JL, Judd RL, Ziegler MH, Medon PJ, Keller WJ. J Nat Prod 1995;58:1285. w3x Braga R. Plantas do Nordeste, especialmente do Ceara. ´ Fortaleza: Ed. Imprensa Nacional, 1976. p. 439. w4x Cabrera GM, Seldes AM. J Nat Prod 1995;58:1920.
Phytochemical communication
Chemical constituents from Tillandsia recurvata ´ de Queirogaa, Lucimara Mariano de Andradea, Marcos Aurelio a ˆ ´ Karina Chagas Florencio , Maria de Fatima Agraa, Marcelo Sobral da Silvaa, Jose´ Maria Barbosa-Filhoa, ˜ da-Cunhaa,b,* Emidio Vasconcelos Leitao a
´ ˆ ´ Laboratorio de Tecnologia Farmaceutica, Universidade Federal da Paraıba, Cx. Postal 5009, ˜ Pessoa, PB, Brazil 58051-970, Joao b ´ ´ Departamento de Farmacia e Biologia, Universidade Estadual da Paraıba, 58100-000, Campina Grande, PB, Brazil Received 12 May 2003; accepted 27 January 2004
Abstract The CHCl3 extract of Tillandsia recurvata yielded 5,39-dihydroxy-6,7,8,49-tetramethoxyflavanone (1), 1,3-di-O-cinnamoyl-glycerol (2) and ethyl ester of caffeic acid. Their structures were elucidated by means of spectroscopic methods such as mass spectroscopy and 1 and 2D-NMR. 䊚 2004 Elsevier B.V. All rights reserved. Keywords: Tillandsia recurvata; 5,39-Dihydroxy-6,7,8,49-tetramethoxyflavanone; 1,3-Di-O-cinnamoylglycerol
Plant. Tillandsia recurvata L. (Bromeliaceae), entire plant collected in September ´ 1999 near the City of Cabaceiras, State of Paraıba, Brazil, where it is popularly known as ‘barba de velho’ (old man’s beard) w1x. A voucher specimen (Agra 2190) is deposited in the Herbarium Prof. Lauro Pires Xavier (JPB) of the Universidade ´ Federal da Paraıba. *Corresponding author. Tel.yfax: q55-83-216-7364. E-mail address: [email protected] (E.V.L. da-Cunha). 0367-326X/04/$ - see front matter 䊚 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.fitote.2004.01.003
424
M.A. de Queiroga et al. / Fitoterapia 75 (2004) 423–425
Uses in traditional medicine. No indications for this species. However, there are indications of medicinal uses of the species T. usneoides as hypoglycemic w2x, anti rheumatic and for liver infections w3x.
Previously isolated constituents. Triterpenoids w4x.
New-isolated constituents. 5,39-Dihydroxy-6,7,8,49-tetramethoxyflavanone (1) 52.0 mg, 1,3-di-O-cinnamoylglycerol (2) 48.5 mg and the ethyl ester of caffeic acid 58.6 mg from 655 g of the plant material.
5,39-Dihydroxy-6,7,8,49-tetramethoxyflavanone (1). Pale yellow oil; 1H-NMR (400-MHz, CDCl3): d 2.84 (1H, dd, J 3.1, 17.2 Hz, H-3 eq), 3.06 (1H, dd, J 12.6, 17.2 Hz, H-3 ax), 3.78 (3H, s, 8-OMe), 3.85 (3H, s, 7-OMe), 3.89 (3H, s, 49OMe), 4.07 (3H, s, 6-OMe), 5.33 (1H, dd, J 3.1, 12.6 Hz, H-2), 6.86 (1H, d, J 8.3 Hz, H-59), 6.92 (1H, dd, J 1.9, 8.3 Hz, H-69), 7.04 (1H, d, J 1.9 Hz, H-29), 11,76 (1H, s, 5-OH); 13C-NMR (100 MHz, CDCl3) d 43.7 (C-3), 56.2 (49-OMe), 61.3 (8-OMe), 61,6 (7-OMe), 61.7 (6-OMe), 79.2 (C-2), 104.4 (C-4a), 110.9 (C-59), 112.8 (C-29), 118,2 (C-69), 131.6 (C-19), 133.4 (C-8), 134.2 (C-6), 146.0 (C-39), 147.2 (C-49), 150.7 (C-8a), 152.0 (C-7), 155.7 (C-5), 197.4 (C-4); EI-MS myz: 376 wMxq (100), 360, 344. 1,3-Di-O-cinnamoylglycerol (2) White amorphous powder; 1H-NMR (400 MHz, CDCl3): d 4.27 (1H, quint, J 5.1 Hz, H-2), 4.36 (2H, dd, J 5.1, 11.6 Hz, H-1a and H-3a), 4.41 (2H, dd, J 5.1, 11.6 Hz, H-1b and H-3b), 6.49 (2H, d, J 16.0 Hz, H39 and H-30), 7.38 (6H, m, H-79, H-70, 89, 80, 99 and 90), 7.52 (4H, m, H-69, H-60, H-109 and H-100), 7.75 (2H, d, J 16.0 Hz, H-49 and H-40); 13C-NMR (100 MHz, CDCl3) d 65.7 (C-1 and C-3), 68.7 (C-2), 117.4 (C-39 and C-30), 128.4 (C-69, C60, C-109 and C-100), 129.1 (C-79, C-70, C-99 and C-90), 130.7 (C-89 and C-80), 134.4 (C-59 and C-50), 146.0 (C-49 and C-40), 167.2 (C-29 and C-20); EI-MS myz 353 wMqHxq, 335, 278, 223, 205 (100).
M.A. de Queiroga et al. / Fitoterapia 75 (2004) 423–425
425
The 1H-NMR and 13C-NMR data for the two substances were assigned by means of one-dimensional and two-dimensional NMR techniques, such as COSY, NOESY, HETCOR and HMBC. Acknowledgments The authors wish to express their sincere thanks to CNPqyIMSEAR for financial support, to the NAPRALERT (SM) database of the University of Illinois-Chicago for the bibliographical information and to Dr A.I. Gray from the University of Strathclyde in Glasgow, Scotland for recording the NMR spectra. References w1x Correa ˆ MP. Dicionario ´ ´ ´ ´ ´ das plantas uteis do Brasil e das exoticas cultivadas. Brasılia: Ministerio da Agricultura, 1984. p. 265. w2x Witherup KM, McLaughlin JL, Judd RL, Ziegler MH, Medon PJ, Keller WJ. J Nat Prod 1995;58:1285. w3x Braga R. Plantas do Nordeste, especialmente do Ceara. ´ Fortaleza: Ed. Imprensa Nacional, 1976. p. 439. w4x Cabrera GM, Seldes AM. J Nat Prod 1995;58:1920.