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Phytochemical constituents of Curcuma amada
Biochemical Systematics and Ecology 44 (2012) 264–266
Contents lists available at SciVerse ScienceDirect
Biochemical Systematics and Ecology journal homepage: www.elsevier.com/locate/biochemsyseco
Phytochemical constituents of Curcuma amada D.B. Alan Sheeja, Mangalam S. Nair* Organic Chemistry Section, Chemical Sciences & Technology Division, CSIR – National Institute for Interdisciplinary Science & Technology, Thiruvananthapuram 695019, Kerala, India
a r t i c l e i n f o Article history: Received 3 January 2012 Accepted 3 June 2012 Available online 28 June 2012 Keywords: Curcuma amada Zingiberaceae (E)-Labda-8(17),12-diene-15,16-dial Coronarin B Coronarin D Zerumin A Zerumin B (E)-Labda-8(17),13-diene-15,16-olide
1. Subject and source Curcuma amada Roxb. is a rhizomatous herb belonging to the genus Curcuma of the Zingiberaceae family and is widespread in India as well as South East Asian countries. The plant is commonly called “mango ginger” since the rhizomes have the smell of raw-mango (The Wealth of India, 2001), a smell that is shared with the related species Curcuma mangga (Abas et al., 2005). The rhizomes of C. amada are used in the traditional systems of medicine especially ‘Ayurveda’ and are reported to have several pharmacological properties (Kirtikar and Basu, 1935; Kapoor, 1990). Due to the combined fresh mango - ginger flavour, the rhizomes are also used extensively in pickles and as a spice. The fresh rhizomes of C. amada used in this study were collected from Kottayam, Kerala. A voucher specimen (TBGT 54688) is deposited in the Tropical Botanical Garden and Research Institute Herbarium, Palode, Kerala, India. 2. Previous work The essential oil of C. amada rhizomes have been studied extensively and the mango flavour has been attributed to d-3carene and cis-ocimene (Gholap and Bandyopadhyay, 1984; Rao et al., 1989). Further, a detailed review of the phytochemical, pharmacological and ethnobotanical studies of the essential oil of mango ginger has been carried out by Jatoi et al. (2007). Anti-inflammatory activity as well as CNS depressant and analgesic activity of the ethanol extract of C. amada rhizome has also been reported (Mujumdar et al., 2000, 2004). Three compounds viz., a labdane diterpenoid (E)-Labda-8(17),12-diene15,16-dial (Singh et al., 2010), a sesquiterpene dimer ‘difurocumenonol’ (Policegoudra et al., 2007a) and a substituted sesquiterpene ‘amadannulen’ (Policegoudra et al., 2007b) have been reported from C. amada. * Corresponding author. Tel.: þ91 471 2515277; fax: þ91 471 2491712. E-mail address: [email protected] (M.S. Nair). 0305-1978/$ – see front matter Ó 2012 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.bse.2012.06.008
D.B. Alan Sheeja, M.S. Nair / Biochemical Systematics and Ecology 44 (2012) 264–266
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3. Present study Dried ground rhizomes of C. amada (400 g) were subjected to repeated extraction using chloroform at room temperature (27 C) for 3 days. Removal of chloroform under reduced pressure gave 23 g of crude extract. This was subjected to column chromatography (CC) using gradient mixtures of petroleum ether and ethyl acetate of increasing polarity. Thus a total of 182 fractions of 100 ml each were collected and they were pooled together to get 19 fraction pools (FP 1–19) according to the similarities in TLC. FP-5 showing one major compound was subjected to Si gel CC and eluted with 2% EtOAc : petroleum ether to obtain (E)-labda-8(17),12-diene-15,16-dial (1) as the major constituent in 6.9 g, whose structure was confirmed based on spectral details reported in literature (Nakatani et al., 1994). FP-8 on purification using flash column chromatography using the solvents petroleum ether : ethyl acetate (95:5–90:10) yielded two compounds viz., b-sitosterol (7, 11 mg) and (E)-labda8(17)-13-diene-15,16-olide (2, 12 mg) identified based on spectral details and comparison with those reported in literature (Nakano et al., 1982; Zdero et al., 1991; Matsuda et al., 2002). FP-11 on further purification by preparative TLC using 20% ethyl acetate in petroleum ether afforded 59 mg of coronarin B (3), the structure of which was confirmed by comparison with the spectral values reported in the literature (Nakatani et al., 1994; Sy and Brown, 1997). FP-14 on purification using 25% EtOAc : petroleum ether afforded another UV active compound which was further purified by preparative thin layer chromatography using 30% EtOAc : petroleum ether to yield 135 mg of pure compound (4) that was confirmed as coronarin D based on spectroscopic data known in literature (Itokawa et al., 1988a). FP-17 was subjected to flash column chromatography using 30% EtOAc : petroleum ether to yield zerumin A (5, 13 mg) (Xu et al., 1996). Purification of FP-18 using 35% EtOAc : petroleum ether afforded curcumin (8, 6 mg) as yellow needles and zerumin B (6, 12 mg) as white needle like crystals (Xu et al., 1996). Fig. 1 represents the structures of compounds (1) to (6). 4. Chemotaxonomic significance Curcuminoids, as well as other diaryl heptanoids and a large number of mono and sesquiterpenoids have been isolated from various species of Curcuma, but there are fewer reports of labdane diterpenoids. The present investigation of C. amada rhizomes led to the isolation of six labdane type diterpenes 1–6, b-sitosterol and curcumin. This is the first report of the presence of compounds 2–6 in C. amada rhizomes. However, (E)-labda-8(17),12-diene-15,16dial (1) is the major constituent of C. amada and is present in 1.7% of dry weight of rhizomes. This labdane dialdehyde has been reported from four species of Curcuma: C. amada (Singh et al., 2010), Curcuma heyneana (Firman et al., 1988), Curcuma longa (Roth et al., 1998) and C. mangga (Abas et al., 2005). It has also been found in many members of the genus Alpinia (Itokawa
Fig. 1. Structures of (E)-labda-8(17),12-diene-15,16-dial (1), (E)-Labda-8(17),13-diene-15,16-olide (2), Coronarin B (3), Coronarin D (4), Zerumin A (5) and Zerumin B (6) isolated from the rhizomes of Curcuma amada.
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et al., 1980, 1988b; Morita and Itokawa, 1988; Sirat et al., 1994; Sy and Brown, 1997; Ngo and Brown, 1998; Nuntawong and Susksamrarn, 2008) as well as Hedychium coronarium (Itokawa et al., 1988a), Zingiber ottensii (Akiyama et al., 2006), Renealmia alpinia (Zhou et al., 1997), Aframomum daniellii (Kimbu et al., 1987) and Aframomum sceptrum (Duker-Eshun et al., 2002). This suggests close genetic relations between the genera Curcuma, Alpinia, Hedychium, Zingiber, Renealmia and Aframomum which belongs to the Zingiberaceae family. Compound (2) characterised as (E)-labda-8(17),13-diene-15,16-olide has only been previously reported from one species of Zingiberaceae, H. coronarium (Matsuda et al., 2002), whereas coronarin B (3) has been isolated from H. coronarium (Itokawa et al., 1988a), Alpinia chinensis (Sy and Brown, 1997), A. sceptrum (Duker-Eshun et al., 2002) and Z. ottensii (Akiyama et al., 2006). Coronarin D (4) has been isolated from H. coronarium (Itokawa et al., 1988a) and Z. ottensii (Akiyama et al., 2006). Zerumin A (5) has been isolated from Alpinia zerumbet (Xu et al., 1996), Alpinia calcarata (Kong et al., 2000) and Z. ottensii (Akiyama et al., 2006). Zerumin B (6) has been obtained from A. zerumbet (Xu et al., 1996) and C. mangga (Abas et al., 2005). To the best of our knowledge, coronarin B (3), coronarin D (4) and zerumin A (5) have not been reported in any species of the genus Curcuma. This could be of systematic importance and the findings suggest that compounds (1), (3), (4) and (5) can be considered as chemotaxonomic markers for C. amada. Acknowledgement Alan Sheeja D. B thanks CSIR, New Delhi for financial assistance in the form of Junior and Senior Research Fellowships. References Abas, A., Lajis, N.H., Shaari, K., Israf, D.A., Stanslas, J., Yusuf, U.K., Raof, S.M., 2005. J. Nat. Prod. 68, 1090. Akiyama, K., Kikuzaki, H., Aoki, T., Okuda, A., Lajis, N.H., Nakatani, N., 2006. J. Nat. Prod. 69, 1637. Duker-Eshun, G., Jaroszewski, J.W., Asomaning, W.M., Oppong-Boachie, F., Olsen, C.E., Christiensen, S.B., 2002. Planta Med. 68, 642. Firman, K., Kinoshita, T., Itai, K., Sankawa, U., 1988. Phytochemistry 27, 3887. Gholap, A.S., Bandyopadhyay, C., 1984. J. Agric. Food Chem. 32, 57. Itokawa, H., Morita, H., Mihashi, S., 1980. Chem. Pharm. Bull. 28, 3452. Itokawa, H., Morita, H., Katou, I., Takeya, K., Cavalheiro, A.J., de Oliveira, R.C.B., Ishige, M., Motidome, M., 1988a. Planta Med. 54, 311. Itokawa, H., Yoshimoto, S., Morita, H., 1988b. Phytochemistry 27, 435. Jatoi, S.A., Kikuchi, A., Gilani, S.A., Watanabe, K.N., 2007. Phytother. Res. 21, 507. Kapoor, L.D., 1990. CRC Handbook of Ayurvedic Medicinal Plants. CRC Press, Boca Raton, FL. Kimbu, S.F., Ngadjui, B.T., Sondengam, B.L., Njimi, T., Connolly, J.D., Fakunle, C.O., 1987. J. Nat. Prod. 50, 230. Kirtikar, K.R., Basu, B.D., 1935. Indian Medicinal Plants, vol. IV. Latin Mohan Basu, Allahabad, p. 2422. Kong, L.-Y., Qin, M.-J., Niwa, M., 2000. J. Nat. Prod. 63, 939. Matsuda, H., Morikawa, T., Sakamoto, Y., Toguchida, I., Yoshikawa, M., 2002. Biorg. Med. Chem. 10, 2527. Morita, H., Itokawa, H., 1988. Planta Med. 54, 117. Mujumdar, A.M., Naik, D.G., Dandge, C.N., Puntambekar, H.M., 2000. Indian J. Pharmacol. 32, 375. Mujumdar, A.M., Naik, D.G., Misar, A.V., Dandge, C.N., Puntambekar, H.M., 2004. Pharm. Biol. 42, 542. Nakatani, N., Kikuzaki, H., Yamaji, H., Yoshio, K., Kitora, C., Okada, K., Padolina, W.G., 1994. Phytochemistry 37, 1383. Ngo, K.-S., Brown, G.D., 1998. Phytochemistry 47, 1117. Nakano, T., Martin, A., Rojas, A., 1982. Tetrahedron 38, 1217. Nuntawong, N., Susksamrarn, A., 2008. Biochem. Syst. Ecol. 36, 661. Policegoudra, R.S., Divakar, S., Aradhya, S.M., 2007a. J. Appl. Microbiol. 102, 1594. Policegoudra, R.S., Abiraj, K., Gowda, D.C., Aradhya, S.M., 2007b. J. Chromatogr. B 852, 40. Rao, A.S., Rajanikanth, B., Seshadri, R., 1989. J. Agric. Food Chem. 37, 740. Roth, G.N., Chandra, A., Nair, M.G., 1998. J. Nat. Prod. 61, 542. Singh, S., Kumar, J.K., Saikia, D., Shanker, K., Thakur, J.P., Negi, A.S., Banerjee, S., 2010. Eur. J. Med. Chem. 45, 4379. Sirat, H.M., Masri, D., Rahman, A.A., 1994. Phytochemistry 36, 699. Sy, L.-K., Brown, G.D., 1997. J. Nat. Prod. 60, 904. The Wealth of India, 2001. A Dictionary of Indian Raw Materials and Industrial Products, vol. 2, p. 259. Xu, H.-X., Dong, H., Sim, K.-Y., 1996. Phytochemistry 42, 149. Zdero, C., Bohlmann, F., Mongal, G.M., 1991. Phytochemistry 30, 3297. Zhou, B.–N., Baj, N.J., Glass, T.E., Malone, S., Werkhoven, M.C.M., Troon, F.V., David, M., Wisse, J.H., Kingston, D.G.I., 1997. J. Nat. Prod. 60, 1287.
Contents lists available at SciVerse ScienceDirect
Biochemical Systematics and Ecology journal homepage: www.elsevier.com/locate/biochemsyseco
Phytochemical constituents of Curcuma amada D.B. Alan Sheeja, Mangalam S. Nair* Organic Chemistry Section, Chemical Sciences & Technology Division, CSIR – National Institute for Interdisciplinary Science & Technology, Thiruvananthapuram 695019, Kerala, India
a r t i c l e i n f o Article history: Received 3 January 2012 Accepted 3 June 2012 Available online 28 June 2012 Keywords: Curcuma amada Zingiberaceae (E)-Labda-8(17),12-diene-15,16-dial Coronarin B Coronarin D Zerumin A Zerumin B (E)-Labda-8(17),13-diene-15,16-olide
1. Subject and source Curcuma amada Roxb. is a rhizomatous herb belonging to the genus Curcuma of the Zingiberaceae family and is widespread in India as well as South East Asian countries. The plant is commonly called “mango ginger” since the rhizomes have the smell of raw-mango (The Wealth of India, 2001), a smell that is shared with the related species Curcuma mangga (Abas et al., 2005). The rhizomes of C. amada are used in the traditional systems of medicine especially ‘Ayurveda’ and are reported to have several pharmacological properties (Kirtikar and Basu, 1935; Kapoor, 1990). Due to the combined fresh mango - ginger flavour, the rhizomes are also used extensively in pickles and as a spice. The fresh rhizomes of C. amada used in this study were collected from Kottayam, Kerala. A voucher specimen (TBGT 54688) is deposited in the Tropical Botanical Garden and Research Institute Herbarium, Palode, Kerala, India. 2. Previous work The essential oil of C. amada rhizomes have been studied extensively and the mango flavour has been attributed to d-3carene and cis-ocimene (Gholap and Bandyopadhyay, 1984; Rao et al., 1989). Further, a detailed review of the phytochemical, pharmacological and ethnobotanical studies of the essential oil of mango ginger has been carried out by Jatoi et al. (2007). Anti-inflammatory activity as well as CNS depressant and analgesic activity of the ethanol extract of C. amada rhizome has also been reported (Mujumdar et al., 2000, 2004). Three compounds viz., a labdane diterpenoid (E)-Labda-8(17),12-diene15,16-dial (Singh et al., 2010), a sesquiterpene dimer ‘difurocumenonol’ (Policegoudra et al., 2007a) and a substituted sesquiterpene ‘amadannulen’ (Policegoudra et al., 2007b) have been reported from C. amada. * Corresponding author. Tel.: þ91 471 2515277; fax: þ91 471 2491712. E-mail address: [email protected] (M.S. Nair). 0305-1978/$ – see front matter Ó 2012 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.bse.2012.06.008
D.B. Alan Sheeja, M.S. Nair / Biochemical Systematics and Ecology 44 (2012) 264–266
265
3. Present study Dried ground rhizomes of C. amada (400 g) were subjected to repeated extraction using chloroform at room temperature (27 C) for 3 days. Removal of chloroform under reduced pressure gave 23 g of crude extract. This was subjected to column chromatography (CC) using gradient mixtures of petroleum ether and ethyl acetate of increasing polarity. Thus a total of 182 fractions of 100 ml each were collected and they were pooled together to get 19 fraction pools (FP 1–19) according to the similarities in TLC. FP-5 showing one major compound was subjected to Si gel CC and eluted with 2% EtOAc : petroleum ether to obtain (E)-labda-8(17),12-diene-15,16-dial (1) as the major constituent in 6.9 g, whose structure was confirmed based on spectral details reported in literature (Nakatani et al., 1994). FP-8 on purification using flash column chromatography using the solvents petroleum ether : ethyl acetate (95:5–90:10) yielded two compounds viz., b-sitosterol (7, 11 mg) and (E)-labda8(17)-13-diene-15,16-olide (2, 12 mg) identified based on spectral details and comparison with those reported in literature (Nakano et al., 1982; Zdero et al., 1991; Matsuda et al., 2002). FP-11 on further purification by preparative TLC using 20% ethyl acetate in petroleum ether afforded 59 mg of coronarin B (3), the structure of which was confirmed by comparison with the spectral values reported in the literature (Nakatani et al., 1994; Sy and Brown, 1997). FP-14 on purification using 25% EtOAc : petroleum ether afforded another UV active compound which was further purified by preparative thin layer chromatography using 30% EtOAc : petroleum ether to yield 135 mg of pure compound (4) that was confirmed as coronarin D based on spectroscopic data known in literature (Itokawa et al., 1988a). FP-17 was subjected to flash column chromatography using 30% EtOAc : petroleum ether to yield zerumin A (5, 13 mg) (Xu et al., 1996). Purification of FP-18 using 35% EtOAc : petroleum ether afforded curcumin (8, 6 mg) as yellow needles and zerumin B (6, 12 mg) as white needle like crystals (Xu et al., 1996). Fig. 1 represents the structures of compounds (1) to (6). 4. Chemotaxonomic significance Curcuminoids, as well as other diaryl heptanoids and a large number of mono and sesquiterpenoids have been isolated from various species of Curcuma, but there are fewer reports of labdane diterpenoids. The present investigation of C. amada rhizomes led to the isolation of six labdane type diterpenes 1–6, b-sitosterol and curcumin. This is the first report of the presence of compounds 2–6 in C. amada rhizomes. However, (E)-labda-8(17),12-diene-15,16dial (1) is the major constituent of C. amada and is present in 1.7% of dry weight of rhizomes. This labdane dialdehyde has been reported from four species of Curcuma: C. amada (Singh et al., 2010), Curcuma heyneana (Firman et al., 1988), Curcuma longa (Roth et al., 1998) and C. mangga (Abas et al., 2005). It has also been found in many members of the genus Alpinia (Itokawa
Fig. 1. Structures of (E)-labda-8(17),12-diene-15,16-dial (1), (E)-Labda-8(17),13-diene-15,16-olide (2), Coronarin B (3), Coronarin D (4), Zerumin A (5) and Zerumin B (6) isolated from the rhizomes of Curcuma amada.
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D.B. Alan Sheeja, M.S. Nair / Biochemical Systematics and Ecology 44 (2012) 264–266
et al., 1980, 1988b; Morita and Itokawa, 1988; Sirat et al., 1994; Sy and Brown, 1997; Ngo and Brown, 1998; Nuntawong and Susksamrarn, 2008) as well as Hedychium coronarium (Itokawa et al., 1988a), Zingiber ottensii (Akiyama et al., 2006), Renealmia alpinia (Zhou et al., 1997), Aframomum daniellii (Kimbu et al., 1987) and Aframomum sceptrum (Duker-Eshun et al., 2002). This suggests close genetic relations between the genera Curcuma, Alpinia, Hedychium, Zingiber, Renealmia and Aframomum which belongs to the Zingiberaceae family. Compound (2) characterised as (E)-labda-8(17),13-diene-15,16-olide has only been previously reported from one species of Zingiberaceae, H. coronarium (Matsuda et al., 2002), whereas coronarin B (3) has been isolated from H. coronarium (Itokawa et al., 1988a), Alpinia chinensis (Sy and Brown, 1997), A. sceptrum (Duker-Eshun et al., 2002) and Z. ottensii (Akiyama et al., 2006). Coronarin D (4) has been isolated from H. coronarium (Itokawa et al., 1988a) and Z. ottensii (Akiyama et al., 2006). Zerumin A (5) has been isolated from Alpinia zerumbet (Xu et al., 1996), Alpinia calcarata (Kong et al., 2000) and Z. ottensii (Akiyama et al., 2006). Zerumin B (6) has been obtained from A. zerumbet (Xu et al., 1996) and C. mangga (Abas et al., 2005). To the best of our knowledge, coronarin B (3), coronarin D (4) and zerumin A (5) have not been reported in any species of the genus Curcuma. This could be of systematic importance and the findings suggest that compounds (1), (3), (4) and (5) can be considered as chemotaxonomic markers for C. amada. Acknowledgement Alan Sheeja D. B thanks CSIR, New Delhi for financial assistance in the form of Junior and Senior Research Fellowships. References Abas, A., Lajis, N.H., Shaari, K., Israf, D.A., Stanslas, J., Yusuf, U.K., Raof, S.M., 2005. J. Nat. Prod. 68, 1090. Akiyama, K., Kikuzaki, H., Aoki, T., Okuda, A., Lajis, N.H., Nakatani, N., 2006. J. Nat. Prod. 69, 1637. Duker-Eshun, G., Jaroszewski, J.W., Asomaning, W.M., Oppong-Boachie, F., Olsen, C.E., Christiensen, S.B., 2002. Planta Med. 68, 642. Firman, K., Kinoshita, T., Itai, K., Sankawa, U., 1988. Phytochemistry 27, 3887. Gholap, A.S., Bandyopadhyay, C., 1984. J. Agric. Food Chem. 32, 57. Itokawa, H., Morita, H., Mihashi, S., 1980. Chem. Pharm. Bull. 28, 3452. Itokawa, H., Morita, H., Katou, I., Takeya, K., Cavalheiro, A.J., de Oliveira, R.C.B., Ishige, M., Motidome, M., 1988a. Planta Med. 54, 311. Itokawa, H., Yoshimoto, S., Morita, H., 1988b. Phytochemistry 27, 435. Jatoi, S.A., Kikuchi, A., Gilani, S.A., Watanabe, K.N., 2007. Phytother. Res. 21, 507. Kapoor, L.D., 1990. CRC Handbook of Ayurvedic Medicinal Plants. CRC Press, Boca Raton, FL. Kimbu, S.F., Ngadjui, B.T., Sondengam, B.L., Njimi, T., Connolly, J.D., Fakunle, C.O., 1987. J. Nat. Prod. 50, 230. Kirtikar, K.R., Basu, B.D., 1935. Indian Medicinal Plants, vol. IV. Latin Mohan Basu, Allahabad, p. 2422. Kong, L.-Y., Qin, M.-J., Niwa, M., 2000. J. Nat. Prod. 63, 939. Matsuda, H., Morikawa, T., Sakamoto, Y., Toguchida, I., Yoshikawa, M., 2002. Biorg. Med. Chem. 10, 2527. Morita, H., Itokawa, H., 1988. Planta Med. 54, 117. Mujumdar, A.M., Naik, D.G., Dandge, C.N., Puntambekar, H.M., 2000. Indian J. Pharmacol. 32, 375. Mujumdar, A.M., Naik, D.G., Misar, A.V., Dandge, C.N., Puntambekar, H.M., 2004. Pharm. Biol. 42, 542. Nakatani, N., Kikuzaki, H., Yamaji, H., Yoshio, K., Kitora, C., Okada, K., Padolina, W.G., 1994. Phytochemistry 37, 1383. Ngo, K.-S., Brown, G.D., 1998. Phytochemistry 47, 1117. Nakano, T., Martin, A., Rojas, A., 1982. Tetrahedron 38, 1217. Nuntawong, N., Susksamrarn, A., 2008. Biochem. Syst. Ecol. 36, 661. Policegoudra, R.S., Divakar, S., Aradhya, S.M., 2007a. J. Appl. Microbiol. 102, 1594. Policegoudra, R.S., Abiraj, K., Gowda, D.C., Aradhya, S.M., 2007b. J. Chromatogr. B 852, 40. Rao, A.S., Rajanikanth, B., Seshadri, R., 1989. J. Agric. Food Chem. 37, 740. Roth, G.N., Chandra, A., Nair, M.G., 1998. J. Nat. Prod. 61, 542. Singh, S., Kumar, J.K., Saikia, D., Shanker, K., Thakur, J.P., Negi, A.S., Banerjee, S., 2010. Eur. J. Med. Chem. 45, 4379. Sirat, H.M., Masri, D., Rahman, A.A., 1994. Phytochemistry 36, 699. Sy, L.-K., Brown, G.D., 1997. J. Nat. Prod. 60, 904. The Wealth of India, 2001. A Dictionary of Indian Raw Materials and Industrial Products, vol. 2, p. 259. Xu, H.-X., Dong, H., Sim, K.-Y., 1996. Phytochemistry 42, 149. Zdero, C., Bohlmann, F., Mongal, G.M., 1991. Phytochemistry 30, 3297. Zhou, B.–N., Baj, N.J., Glass, T.E., Malone, S., Werkhoven, M.C.M., Troon, F.V., David, M., Wisse, J.H., Kingston, D.G.I., 1997. J. Nat. Prod. 60, 1287.