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Benzoxazinones from Acanthus ilicifolius
Biochemical Systematics and Ecology 33 (2005) 643–645 www.elsevier.com/locate/biochemsyseco
Benzoxazinones from Acanthus ilicifolius Chang-Hong Huoa, Bin Wanga, Wen-Han Linb, Yu-Ying Zhaoa,* a
Department of Natural Medicines, School of Pharmaceutical Sciences, Peking University, No. 38 Xueyuan Road, Beijing 100083, PR China b State Key Laboratory of Natural and Biomimetic Drugs, Peking University, No. 38 Xueyuan Road, Beijing 100083, PR China Received 20 March 2004; accepted 16 October 2004
Keywords: Acanthus ilicifolius; Acanthus; Acanthaceae; Benzoxazinones; Chemotaxonomy
1. Subject and source Acanthus ilicifolius Linn (Family: Acanthaceae) is a spiny herb distributed in the mangroves of southeastern Asia. Plant material was collected during December 2002 in Sanya, Hainan province, China. A voucher specimen (No. HH-03) is deposited in the herbarium of the School of Pharmaceutical Sciences, Peking University.
2. Previous work Not more than 30 different plant secondary metabolites, notably, lignans, phenylethanoid glycosides, flavonoids, triterpenoids, phytosterols, megastigmane
* Corresponding author. Tel./fax: C86 10 82801592. E-mail address: [email protected] (Y.-Y. Zhao). 0305-1978/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.bse.2004.11.002
644
C.-H. Huo et al. / Biochemical Systematics and Ecology 33 (2005) 643–645
glucosides and benzoxazinones: benzoxazolinone (BOA) (1), (2R)-2-O-b-D-glucopyranosyl-2H-1,4-benzoxazin-3(4H )-one (HBOA-Glc) (2), (2R)-2-O-b-D-glucopyranosyl-4-hydroxy-2H-1,4-benzoxazin-3(4H )-one (DIBOA-Glc) (3), 7-Cl-(2R)-2-O-bD-glucopyranosyl-2H-1,4-benzoxazin-3(4H )-one (4), (2R)-2-O-b-D-glucopyranosyl7-hydroxy-2H-1,4-benzoxazin-3(4H )-one, (2R)-2-O-b-D-glucopyranosyl-5-hydroxy2H-1,4-benzoxazin-3(4H )-one have previously been reported from the aerial parts of A. ilicifolius (Kanchanapoom et al., 2001a,b; Wu et al., 2003a,b; Minocha and Tiwari, 1980; Nair and Ramachandran, 1987; Amitabha et al., 1985; Murty and Kamat, 1984). From the extract of the roots, BOA, stigmasterol and its glucoside were reported (Kokpol and Chittawong, 1986).
3. Present study Dried and powdered roots of A. ilicifolius (2 kg) were extracted with 95% EtOH at room temperature. The EtOH extract was suspended in water and then successively extracted with petroleum ether, EtOAc and n-BuOH. The EtOAc extract was subjected to silica gel column chromatography using CHCl3–Me2CO (100:0 / 92:8) as eluent, BOA (1, 180 mg) (Murty and Kamat, 1984; Chatterjee et al., 1990), HBOA [2-hydroxy-2H-1,4-benzoxazin-3(4H )-one] (5, 312 mg) and DIBOA [2,4-dihydroxy-2H-1,4-benzoxazin-3(4H )-one] (6, 610 mg) (Atkinson et al., 1991) were isolated as main constituents by crystallisation. The n-BuOH extract was subjected to column chromatography of HP20, and eluted with H2O, 10% MeOH, 30% MeOH, 60% MeOH and MeOH, successively. The fraction eluted with 10% MeOH was chromatographed on Sephadex LH-20 and TLC to give compounds 2 (42 mg), 3 (20 mg) and 4 (5 mg) (Kanchanapoom et al., 2001b). The obtained spectral data of the isolated compounds were in agreement with the appropriate literature data.
4. Chemotaxonomic significance The isolation of HBOA is reported now for the first time in a plant of the genus Acanthus. To the best of our knowledge, HBOA has only been identified before from Blepharis sindica (Acanthaceae) (Ahmad et al., 1984) and from Scoparia dulcis (Scrophulariaceae) (Pratt et al., 1995). On the other hand, this is the first report of DIBOA in A. ilicifolius, although it has been reported from dicotyledonous species, in Consolida orientalis (Ranunculaceae) (Ozden, et al., 1992), S. dulcis (Scrophulariaceae), and in six Acanthaceae species: Acanthus mollis, Acanthus spinosus, Aphelandra aurantiaca, Aphelandra squarrosa, Crossandra infundibuliformis, Crossandra pungens (Pratt et al., 1995). In dicotyledonous plants, BOA has also been isolated from Blepharis edulis (Chatterjee et al., 1990), A. mollis (Wolf et al., 1985), A. aurantiaca (Acanthaceae) and S. dulcis (Scrophulariaceae) (Pratt et al., 1995). HBOA-Glc has also been reported in two other Acanthaceae species: B. edulis (Chatterjee et al., 1990) and Acanthus ebracteatus (Kanchanapoom et al., 2001c),
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while DIBOA-Glc has also been reported in the same genus species: A. mollis (Wolf et al., 1985) and A. ebracteatus (Kanchanapoom et al., 2001b). The distribution of compounds 1–6 in all parts of A. ilicifolius indicates that benzoxazinones may be useful as chemotoxonomic markers in the Acanthus genus. The presence of BOA, HBOA and DIBOA in both the Acanthaceae family and the Scrophulariaceae family is in agreement with the conclusion that taxonomically Acanthaceae and Scrophulariaceae are closely related families in the order Scrophulariales (Pratt et al., 1995). Additionally, the occurrence of BOA, HBOA and HBOA-Glc in the genus Acanthus and the genus Blepharis, which is a member of the same family (Acanthaceae), may imply a close relationship between the two genera.
Acknowledgements This work is supported by Marine 863 Project (2003AA624030). The identification of the plant material was carried out by Prof. Hu-Biao Chen, Department of Natural Medicines, School of Pharmaceutical Sciences, Peking University.
References Ahmad, V.U., Burki, A.M., Mahmood, I., Smith, D.L., 1984. J. Chem. Soc. Pak. 6, 217. Amitabha, G., Suniti, M., Ashis, K., Choudhurg, A., 1985. Phytochemistry 24, 1725. Atkinson, J., Morand, P., Arnason, J.T., 1991. J. Org. Chem. 56, 1788. Chatterjee, A., Sharma, N.J., Banerji, J., Basa, S.C., 1990. Indian J. Chem. 29B, 132. Kanchanapoom, T., Kamel, M.S., Kasai, R., Yamasaki, K., Picheansoonthon, C., Hiraga, Y., 2001a. Phytochemistry 56, 369. Kanchanapoom, T., Kamel, M.S., Kasai, R., Picheansoonthon, C., Hiraga, Y., Yamasaki, K., 2001b. Phytochemistry 58, 637. Kanchanapoom, T., Kasai, R., Picheansoonthon, C., Yamasaki, K., 2001c. Phytochemistry 58, 811. Kokpol, U., Chittawong, V., 1986. J. Nat. Prod. 49, 355. Minocha, P.K., Tiwari, K.P., 1980. Pol. J. Chem. 54, 2089. Murty, M.S.R., Kamat, S.Y., 1984. Indian J. Pharm. Sci. 46, 218. Nair, A.G., Ramachandran, P.V., 1987. J. Indian Chem. Soc. 64, 228. Ozden, S., Ozden, T., Attila, I., Kucukislamoglu, M., Okatan, A., 1992. J. Chromatogr. 609, 402. Pratt, K., Kumar, P., Chilton, W.S., 1995. Biochem. Syst. Ecol. 23, 781. Wolf, R.B., Spencer, G.F., Plattner, R.D., 1985. J. Nat. Prod. 48, 59. Wu, J., Zhang, S., Xiao, Q., Li, Q.-X., Huang, J.-S., Long, L.-J., Huang, L.-M., 2003a. Pharmazie 58, 363. Wu, J., Zhang, S., Xiao, Q., Li, Q.-X., Huang, J.-S., Long, L.-J., Huang, L.-M., 2003b. Phytochemistry 63, 491.
Benzoxazinones from Acanthus ilicifolius Chang-Hong Huoa, Bin Wanga, Wen-Han Linb, Yu-Ying Zhaoa,* a
Department of Natural Medicines, School of Pharmaceutical Sciences, Peking University, No. 38 Xueyuan Road, Beijing 100083, PR China b State Key Laboratory of Natural and Biomimetic Drugs, Peking University, No. 38 Xueyuan Road, Beijing 100083, PR China Received 20 March 2004; accepted 16 October 2004
Keywords: Acanthus ilicifolius; Acanthus; Acanthaceae; Benzoxazinones; Chemotaxonomy
1. Subject and source Acanthus ilicifolius Linn (Family: Acanthaceae) is a spiny herb distributed in the mangroves of southeastern Asia. Plant material was collected during December 2002 in Sanya, Hainan province, China. A voucher specimen (No. HH-03) is deposited in the herbarium of the School of Pharmaceutical Sciences, Peking University.
2. Previous work Not more than 30 different plant secondary metabolites, notably, lignans, phenylethanoid glycosides, flavonoids, triterpenoids, phytosterols, megastigmane
* Corresponding author. Tel./fax: C86 10 82801592. E-mail address: [email protected] (Y.-Y. Zhao). 0305-1978/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.bse.2004.11.002
644
C.-H. Huo et al. / Biochemical Systematics and Ecology 33 (2005) 643–645
glucosides and benzoxazinones: benzoxazolinone (BOA) (1), (2R)-2-O-b-D-glucopyranosyl-2H-1,4-benzoxazin-3(4H )-one (HBOA-Glc) (2), (2R)-2-O-b-D-glucopyranosyl-4-hydroxy-2H-1,4-benzoxazin-3(4H )-one (DIBOA-Glc) (3), 7-Cl-(2R)-2-O-bD-glucopyranosyl-2H-1,4-benzoxazin-3(4H )-one (4), (2R)-2-O-b-D-glucopyranosyl7-hydroxy-2H-1,4-benzoxazin-3(4H )-one, (2R)-2-O-b-D-glucopyranosyl-5-hydroxy2H-1,4-benzoxazin-3(4H )-one have previously been reported from the aerial parts of A. ilicifolius (Kanchanapoom et al., 2001a,b; Wu et al., 2003a,b; Minocha and Tiwari, 1980; Nair and Ramachandran, 1987; Amitabha et al., 1985; Murty and Kamat, 1984). From the extract of the roots, BOA, stigmasterol and its glucoside were reported (Kokpol and Chittawong, 1986).
3. Present study Dried and powdered roots of A. ilicifolius (2 kg) were extracted with 95% EtOH at room temperature. The EtOH extract was suspended in water and then successively extracted with petroleum ether, EtOAc and n-BuOH. The EtOAc extract was subjected to silica gel column chromatography using CHCl3–Me2CO (100:0 / 92:8) as eluent, BOA (1, 180 mg) (Murty and Kamat, 1984; Chatterjee et al., 1990), HBOA [2-hydroxy-2H-1,4-benzoxazin-3(4H )-one] (5, 312 mg) and DIBOA [2,4-dihydroxy-2H-1,4-benzoxazin-3(4H )-one] (6, 610 mg) (Atkinson et al., 1991) were isolated as main constituents by crystallisation. The n-BuOH extract was subjected to column chromatography of HP20, and eluted with H2O, 10% MeOH, 30% MeOH, 60% MeOH and MeOH, successively. The fraction eluted with 10% MeOH was chromatographed on Sephadex LH-20 and TLC to give compounds 2 (42 mg), 3 (20 mg) and 4 (5 mg) (Kanchanapoom et al., 2001b). The obtained spectral data of the isolated compounds were in agreement with the appropriate literature data.
4. Chemotaxonomic significance The isolation of HBOA is reported now for the first time in a plant of the genus Acanthus. To the best of our knowledge, HBOA has only been identified before from Blepharis sindica (Acanthaceae) (Ahmad et al., 1984) and from Scoparia dulcis (Scrophulariaceae) (Pratt et al., 1995). On the other hand, this is the first report of DIBOA in A. ilicifolius, although it has been reported from dicotyledonous species, in Consolida orientalis (Ranunculaceae) (Ozden, et al., 1992), S. dulcis (Scrophulariaceae), and in six Acanthaceae species: Acanthus mollis, Acanthus spinosus, Aphelandra aurantiaca, Aphelandra squarrosa, Crossandra infundibuliformis, Crossandra pungens (Pratt et al., 1995). In dicotyledonous plants, BOA has also been isolated from Blepharis edulis (Chatterjee et al., 1990), A. mollis (Wolf et al., 1985), A. aurantiaca (Acanthaceae) and S. dulcis (Scrophulariaceae) (Pratt et al., 1995). HBOA-Glc has also been reported in two other Acanthaceae species: B. edulis (Chatterjee et al., 1990) and Acanthus ebracteatus (Kanchanapoom et al., 2001c),
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while DIBOA-Glc has also been reported in the same genus species: A. mollis (Wolf et al., 1985) and A. ebracteatus (Kanchanapoom et al., 2001b). The distribution of compounds 1–6 in all parts of A. ilicifolius indicates that benzoxazinones may be useful as chemotoxonomic markers in the Acanthus genus. The presence of BOA, HBOA and DIBOA in both the Acanthaceae family and the Scrophulariaceae family is in agreement with the conclusion that taxonomically Acanthaceae and Scrophulariaceae are closely related families in the order Scrophulariales (Pratt et al., 1995). Additionally, the occurrence of BOA, HBOA and HBOA-Glc in the genus Acanthus and the genus Blepharis, which is a member of the same family (Acanthaceae), may imply a close relationship between the two genera.
Acknowledgements This work is supported by Marine 863 Project (2003AA624030). The identification of the plant material was carried out by Prof. Hu-Biao Chen, Department of Natural Medicines, School of Pharmaceutical Sciences, Peking University.
References Ahmad, V.U., Burki, A.M., Mahmood, I., Smith, D.L., 1984. J. Chem. Soc. Pak. 6, 217. Amitabha, G., Suniti, M., Ashis, K., Choudhurg, A., 1985. Phytochemistry 24, 1725. Atkinson, J., Morand, P., Arnason, J.T., 1991. J. Org. Chem. 56, 1788. Chatterjee, A., Sharma, N.J., Banerji, J., Basa, S.C., 1990. Indian J. Chem. 29B, 132. Kanchanapoom, T., Kamel, M.S., Kasai, R., Yamasaki, K., Picheansoonthon, C., Hiraga, Y., 2001a. Phytochemistry 56, 369. Kanchanapoom, T., Kamel, M.S., Kasai, R., Picheansoonthon, C., Hiraga, Y., Yamasaki, K., 2001b. Phytochemistry 58, 637. Kanchanapoom, T., Kasai, R., Picheansoonthon, C., Yamasaki, K., 2001c. Phytochemistry 58, 811. Kokpol, U., Chittawong, V., 1986. J. Nat. Prod. 49, 355. Minocha, P.K., Tiwari, K.P., 1980. Pol. J. Chem. 54, 2089. Murty, M.S.R., Kamat, S.Y., 1984. Indian J. Pharm. Sci. 46, 218. Nair, A.G., Ramachandran, P.V., 1987. J. Indian Chem. Soc. 64, 228. Ozden, S., Ozden, T., Attila, I., Kucukislamoglu, M., Okatan, A., 1992. J. Chromatogr. 609, 402. Pratt, K., Kumar, P., Chilton, W.S., 1995. Biochem. Syst. Ecol. 23, 781. Wolf, R.B., Spencer, G.F., Plattner, R.D., 1985. J. Nat. Prod. 48, 59. Wu, J., Zhang, S., Xiao, Q., Li, Q.-X., Huang, J.-S., Long, L.-J., Huang, L.-M., 2003a. Pharmazie 58, 363. Wu, J., Zhang, S., Xiao, Q., Li, Q.-X., Huang, J.-S., Long, L.-J., Huang, L.-M., 2003b. Phytochemistry 63, 491.