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Chemical constituents of Euphorbia kansui
Biochemical Systematics and Ecology 43 (2012) 64–66
Contents lists available at SciVerse ScienceDirect
Biochemical Systematics and Ecology journal homepage: www.elsevier.com/locate/biochemsyseco
Chemical constituents of Euphorbia kansui Qing Peng a, Guoyu Li b, c, Yueping Ma a, d, Jian Huang a, d, Xiuyan Wei a, d, Jinhui Wang a, b, c, d, * a
School of Traditional Chinese Materia Medica, Shenyang Pharmaceutical University, Shenyang 110016, PR China School of Pharmacy, Shihezi University, Shihezi 832002, PR China Key Laboratory of Phytomedicine Resources & Modernization of TCM of Ministry of Education, Shihezi 832002, PR China d Key Laboratory of Structure-Based Drug Design & Discovery of Ministry of Education, Shenyang Pharmaceutical University, Shenyang 110016, PR China b c
a r t i c l e i n f o
a b s t r a c t
Article history: Received 1 September 2011 Accepted 26 February 2012 Available online 28 March 2012
Phytochemical investigation of the dried roots of Euphorbia kansui resulted in the isolation of three flavonoids (1–3), three diterpenoids (4–6) and five triterprnoids (7–11). Among them, three compounds (1–3) were firstly isolated from the family Euphorbiaceae. Others were reported in the genus Euphorbia, in which three compounds (8–11) were firstly isolated from the E. kansui. The chemotaxonomic significance of these compounds was summarized. Ó 2012 Elsevier Ltd. All rights reserved.
Keywords: Euphorbia kansui Euphorbiaceae Chalcones Flavanones Diterpenoids Triterpenoids
1. Subject and source The genus Euphorbia belongs to the family Euphorbiaceae with about 2000 species, mainly distributed in tropical and subtropical regions of the world. The records show 32 species in genus Euphorbia are used as medicine in Dictionary of Chinese Traditional Drugs. The dried roots of Euphorbia kansui have been used as a herbal remedy for edema, ascites and cancers, locally known as “Gan sui” in Chinese Traditional Medicine (Dictionary of Chinese Traditional Drugs, 1977). The dried roots of E. kansui were collected from Shanxi Province, P. R. China, and identified by Prof. Jincai Lu (Shenyang Pharmaceutical University). A voucher specimen (20100605) has been deposited in the Herbarium of the Shenyang Pharmaceutical University. 2. Previous work Previous phytochemical investigations on the genus Euphorbia have demonstrated the presence of several types of compounds including diterpenoids, triterpenoids, flavonoids, steroids, and phenolic derivatives. A lot of chemical compounds with activities showed above have already been isolated from E. kansui and identified, including diterpenoids (Uemura et al., 1974), triterpenoids (Wang et al., 2003), and phenolic derivatives (Ding and Jia, 1992). However, there are no reports in the isolation of flavonoids from E. kansui. * Corresponding author. School of Traditional Chinese Materia Medica, Shenyang Pharmaceutical University, Shenyang, PR China. Tel.: þ86 024 23986479. E-mail address: [email protected] (J. Wang). 0305-1978/$ – see front matter Ó 2012 Elsevier Ltd. All rights reserved. doi:10.1016/j.bse.2012.02.021
Q. Peng et al. / Biochemical Systematics and Ecology 43 (2012) 64–66
65
3. Present study Dry roots of E. kansui (5.0 kg) were refluxed three times with 95% EtOH and concentrated under reduced pressure to give a crude extract (323 g). The extract suspended in H2O was subjected to a HPD100 macroporous resin gel column, eluting with H2O, 65% EtOH and 90% EtOH, successively to give three different polar parts. The 90% EtOH portion (57.5 g) was subjected to silica gel column chromatography (CC) with a gradient of petroleum ether/acetone (100:1–100:100) to give fractions 1–12. Compound 6 (15.0 mg), 7 (13.1 mg), 8 (5.4 mg) and 9 (8.2 mg) were isolated from fraction 2, respectively, by repeated silica gel CC eluted with petroleum ether/EtOAc/acetone and recrystallization. Fraction 3 was subjected to Sephadex LH-20 CC eluted with CHCl3/MeOH (1:1) to afford 2 (33.2 mg), whilst fraction 6 contained 1 (9.5 mg) and 3 (11.7 mg). Fraction 4 repeatedly applied to silica gel CC and ODS CC, and purified by preparative reverse phase high pressure liquid chromatography (RP-HPLC) to yield 4 (38.0 mg) and 5 (73.5 mg). In the same manner, 10 (48.5 mg) and 11 (7.5 mg) were obtained from fraction 7. The UV, ESI-TOF-MS, 1 D-, 2 D- NMR spectra of compounds 1–11 (Fig. 1) were measured, and comparison with the literature data revealed the following identities: 20 ,40 -dihydroxy-60 -methoxy-30 -menthylchalcone (1) (Anjaneyulu and Raju, 1984), 20 ,40 -dihydroxy-60 -methoxy-30 ,50 -dimenthylchalcone (2) (Malterud et al., 1977), (2S)-7-hydroxy-5-methoxy-6,8dimenthylflavanone (3) (Mitscher et al., 1973), 5-O-benzoyl-3b-hydroxy-20-deoxyingenol (4) (Uemura et al., 1974), 3-Obenzoyl-3b-hydroxy-20-deoxyingenol (5) (Uemura et al., 1974), 4-O-acetyl-5-O-benzoyl-3b-hydroxy-20-deoxyingenol (6) (Li
CH 3
R OCH 3
HO
HO
O
H 3C
H 3C OH
OCH 3
O
1R=H 2 R = CH3
O
3
O R1 R2 R3
H
H HO
4 R1 = OH, R2 = OH, R3 = OBz 5 R1 = OBz, R2 = OH, R3 = OH 6 R1 = OH, R2 = OAc, R3 = OBz
7
R
HO
R
HO
8 R = CH3 10 R = COOH
9 R = CH3 11 R = COOH Fig. 1. Structures of compounds 1–11.
66
Q. Peng et al. / Biochemical Systematics and Ecology 43 (2012) 64–66
et al., 2008), euphol (7) (Gewali et al., 1990), a-amyrin (8) (Mahato and Kundu, 1994), b-amyrin (9) (Tanaka and Matsunaga, 1989), oleanolic acid (10) (Ikuta and Itokawa, 1988), and ursolic acid (11) (Deng et al., 1999). 4. Chemotaxonomic significance In the present study, two chalcones (1 and 2), one flavanone (3), three diterpenoids (4–6) and five triterpenoids (7–11) were obtained from the dry roots of E. kansui (Fig. 1). Compound 7 is a common component in genus Euphorbia, as well as in E. kansui (Zheng et al., 1998). Compounds 8 and 9 have been found in many species of genus Euphorbia, and the co-occurrence of 8 and 9 has been reported for Euphorbia trigona (Anjaneyulu and Rao, 1985). Particularly compounds 10 and 11 are more restricted in their distribution and their presence have been note in a few Euphorbia species. Previous research obtained that oleanolic acid (10) was isolated from Euphorbia paralias (Khafagy et al., 1976), Euphorbia dracunculoides Lam (Chawla et al., 1982), Euphorbia abyssinica Gmel (El-Fiky et al., 2008), Euphorbia chrysocoma (Jiang et al., 2009), and ursolic acid (11) was from E. paralias (Khafagy et al., 1976), E. chrysocoma (Shi et al., 2005), Euphorbia hirta (Mallavadhani and Narasimhan, 2009). The pentacyclic triterpenoids (8–11) described here for the first time in E. kansui. The existence of these triterpenoids may indicate a close relationship with the members of the genus Euphorbia on their chemical composition. Compound 4–6, three diterpenoids, which have not been reported in any other species of Euphorbia, have been shown to be good taxonomic markers for E. kansui. Compound 4 has been previously isolated from E. kansui (Uemura et al., 1974), which can convert to compounds 6 through acetylation of 4-OH. Compounds 5 and 6 have been reported in E. kansui (Uemura et al., 1974) and E. kansui Preparata (Li et al., 2008). The present phytochemical investigation on E. kansui was in a good agreement with other reports. Compounds 1–3, belonging to uncommon C-methylated flavonoids, reported from the family Euphorbiaceae for the first time. Previously these two chalcones and one flavanone were frequently isolated from the families Myrtaceae and Myricaceae (Malterud et al., 1977; Wollenweber et al., 1985; Zhang et al., 1990; Le et al., 1997). It is noteworthy that the occurrence of compounds 1–3 as major components in E. kansui may indicate other similarities in the chemistry of the families Euphorbiaceae, Myrtaceae and Myricaceae. In terms of chemotaxonomy, the compounds 1–6 may sever as the specific makers of E. kansui from Shanxi Province, P. R. China. Acknowledgements This work was financially supported by the Fok Ying Tung Education Foundation (No. 101040) & National Major Special Science and Technology Project (2010ZX09401-304-104A). References Anjaneyulu, A.S.R., Raju, S.N., 1984. Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry 23B, 1010. Anjaneyulu, V., Rao, G.S., 1985. Indian Journal of Pharmaceutical Sciences 47, 194. Chawla, H.M., Chakrabarty, K., Chibber, S.S., Kalia, A.N., Chaudhary, N.C., 1982. Science and Culture 48, 203. Deng, J.Z., Starck, S.R., Hecht, S.M., 1999. Journal of Natural Products 62, 1624. “Dictionary of Chinese Traditional Drugs”, vol. 1, Shanghai Science and Technology Press, Shanghai, 1977, 573. Ding, Y.L., Jia, Z.J., 1992. Phytochemistry 31, 1435. El-Fiky, F., Asres, K., Gibbons, S., Hammoda, H., Badr, J., Umer, S., 2008. Natural Product Communications 3, 1505. Gewali, M.B., Hattori, M., Tezuka, Y., Kikuchi, T., Namba, T., 1990. Phytochemistry 29, 1625. Ikuta, A., Itokawa, H., 1988. Phytochemistry 27, 2813. Jiang, C.Y., Mu, S.Z., Deng, B., Ge, Y.H., Zhang, J.X., Hao, X.J., 2009. Journal of Chinese Medicinal Materials 32, 1390. Khafagy, S.M., Gharbo, S.A., Abdel Salam, N.A., 1976. Planta Medica 29, 301. Le, T.A.D., Nguyen, X.D., Hoang, V.L., 1997. Tap Chi Hoa Hoc 35, 47. Li, C.F., Wang, J.H., Cong, Y., Li, X., 2008. Journal of Asian Natural Products Research 10, 101. Mahato, S.B., Kundu, A.P., 1994. Phytochemistry 37, 1517. Mallavadhani, U.V., Narasimhan, K., 2009. Natural Product Research 23 (7), 644–651. Malterud, K.E., Anthonsen, T., Lorentzen, G.B., 1977. Phytochemistry 16, 1805. Mitscher, L.A., Wu, W.N., Beal, J.L., 1973. Lloydia 36, 422. Shi, H.M., Long, B.S., Cui, X.M., Min, Z.D., 2005. Journal of Asian Natural Products Research 7, 857. Tanaka, R., Matsunaga, S., 1989. Phytochemistry 28, 1699. Uemura, D., Ohwaki, H., Hirata, Y., Chen, Y.P., Hsu, H. Yen, 1974. Tetrahedron Letters 29, 2527. Wang, L.Y., Wang, N.L., Yao, X.S., Miyata, S., Kitanaka, S., 2003. Journal of Natural Products 66, 630. Wollenweber, E., Kohorst, G., Mann, K., Bell, J.M., 1985. Journal of Plant Physiology 117, 423. Zhang, F.X., Liu, M.F., Lu, R.R., 1990. Zhiwu Xuebao 32, 469. Zheng, W.F., Cui, Z., Zhu, Q., 1998. Planta Medica 64, 754.
Contents lists available at SciVerse ScienceDirect
Biochemical Systematics and Ecology journal homepage: www.elsevier.com/locate/biochemsyseco
Chemical constituents of Euphorbia kansui Qing Peng a, Guoyu Li b, c, Yueping Ma a, d, Jian Huang a, d, Xiuyan Wei a, d, Jinhui Wang a, b, c, d, * a
School of Traditional Chinese Materia Medica, Shenyang Pharmaceutical University, Shenyang 110016, PR China School of Pharmacy, Shihezi University, Shihezi 832002, PR China Key Laboratory of Phytomedicine Resources & Modernization of TCM of Ministry of Education, Shihezi 832002, PR China d Key Laboratory of Structure-Based Drug Design & Discovery of Ministry of Education, Shenyang Pharmaceutical University, Shenyang 110016, PR China b c
a r t i c l e i n f o
a b s t r a c t
Article history: Received 1 September 2011 Accepted 26 February 2012 Available online 28 March 2012
Phytochemical investigation of the dried roots of Euphorbia kansui resulted in the isolation of three flavonoids (1–3), three diterpenoids (4–6) and five triterprnoids (7–11). Among them, three compounds (1–3) were firstly isolated from the family Euphorbiaceae. Others were reported in the genus Euphorbia, in which three compounds (8–11) were firstly isolated from the E. kansui. The chemotaxonomic significance of these compounds was summarized. Ó 2012 Elsevier Ltd. All rights reserved.
Keywords: Euphorbia kansui Euphorbiaceae Chalcones Flavanones Diterpenoids Triterpenoids
1. Subject and source The genus Euphorbia belongs to the family Euphorbiaceae with about 2000 species, mainly distributed in tropical and subtropical regions of the world. The records show 32 species in genus Euphorbia are used as medicine in Dictionary of Chinese Traditional Drugs. The dried roots of Euphorbia kansui have been used as a herbal remedy for edema, ascites and cancers, locally known as “Gan sui” in Chinese Traditional Medicine (Dictionary of Chinese Traditional Drugs, 1977). The dried roots of E. kansui were collected from Shanxi Province, P. R. China, and identified by Prof. Jincai Lu (Shenyang Pharmaceutical University). A voucher specimen (20100605) has been deposited in the Herbarium of the Shenyang Pharmaceutical University. 2. Previous work Previous phytochemical investigations on the genus Euphorbia have demonstrated the presence of several types of compounds including diterpenoids, triterpenoids, flavonoids, steroids, and phenolic derivatives. A lot of chemical compounds with activities showed above have already been isolated from E. kansui and identified, including diterpenoids (Uemura et al., 1974), triterpenoids (Wang et al., 2003), and phenolic derivatives (Ding and Jia, 1992). However, there are no reports in the isolation of flavonoids from E. kansui. * Corresponding author. School of Traditional Chinese Materia Medica, Shenyang Pharmaceutical University, Shenyang, PR China. Tel.: þ86 024 23986479. E-mail address: [email protected] (J. Wang). 0305-1978/$ – see front matter Ó 2012 Elsevier Ltd. All rights reserved. doi:10.1016/j.bse.2012.02.021
Q. Peng et al. / Biochemical Systematics and Ecology 43 (2012) 64–66
65
3. Present study Dry roots of E. kansui (5.0 kg) were refluxed three times with 95% EtOH and concentrated under reduced pressure to give a crude extract (323 g). The extract suspended in H2O was subjected to a HPD100 macroporous resin gel column, eluting with H2O, 65% EtOH and 90% EtOH, successively to give three different polar parts. The 90% EtOH portion (57.5 g) was subjected to silica gel column chromatography (CC) with a gradient of petroleum ether/acetone (100:1–100:100) to give fractions 1–12. Compound 6 (15.0 mg), 7 (13.1 mg), 8 (5.4 mg) and 9 (8.2 mg) were isolated from fraction 2, respectively, by repeated silica gel CC eluted with petroleum ether/EtOAc/acetone and recrystallization. Fraction 3 was subjected to Sephadex LH-20 CC eluted with CHCl3/MeOH (1:1) to afford 2 (33.2 mg), whilst fraction 6 contained 1 (9.5 mg) and 3 (11.7 mg). Fraction 4 repeatedly applied to silica gel CC and ODS CC, and purified by preparative reverse phase high pressure liquid chromatography (RP-HPLC) to yield 4 (38.0 mg) and 5 (73.5 mg). In the same manner, 10 (48.5 mg) and 11 (7.5 mg) were obtained from fraction 7. The UV, ESI-TOF-MS, 1 D-, 2 D- NMR spectra of compounds 1–11 (Fig. 1) were measured, and comparison with the literature data revealed the following identities: 20 ,40 -dihydroxy-60 -methoxy-30 -menthylchalcone (1) (Anjaneyulu and Raju, 1984), 20 ,40 -dihydroxy-60 -methoxy-30 ,50 -dimenthylchalcone (2) (Malterud et al., 1977), (2S)-7-hydroxy-5-methoxy-6,8dimenthylflavanone (3) (Mitscher et al., 1973), 5-O-benzoyl-3b-hydroxy-20-deoxyingenol (4) (Uemura et al., 1974), 3-Obenzoyl-3b-hydroxy-20-deoxyingenol (5) (Uemura et al., 1974), 4-O-acetyl-5-O-benzoyl-3b-hydroxy-20-deoxyingenol (6) (Li
CH 3
R OCH 3
HO
HO
O
H 3C
H 3C OH
OCH 3
O
1R=H 2 R = CH3
O
3
O R1 R2 R3
H
H HO
4 R1 = OH, R2 = OH, R3 = OBz 5 R1 = OBz, R2 = OH, R3 = OH 6 R1 = OH, R2 = OAc, R3 = OBz
7
R
HO
R
HO
8 R = CH3 10 R = COOH
9 R = CH3 11 R = COOH Fig. 1. Structures of compounds 1–11.
66
Q. Peng et al. / Biochemical Systematics and Ecology 43 (2012) 64–66
et al., 2008), euphol (7) (Gewali et al., 1990), a-amyrin (8) (Mahato and Kundu, 1994), b-amyrin (9) (Tanaka and Matsunaga, 1989), oleanolic acid (10) (Ikuta and Itokawa, 1988), and ursolic acid (11) (Deng et al., 1999). 4. Chemotaxonomic significance In the present study, two chalcones (1 and 2), one flavanone (3), three diterpenoids (4–6) and five triterpenoids (7–11) were obtained from the dry roots of E. kansui (Fig. 1). Compound 7 is a common component in genus Euphorbia, as well as in E. kansui (Zheng et al., 1998). Compounds 8 and 9 have been found in many species of genus Euphorbia, and the co-occurrence of 8 and 9 has been reported for Euphorbia trigona (Anjaneyulu and Rao, 1985). Particularly compounds 10 and 11 are more restricted in their distribution and their presence have been note in a few Euphorbia species. Previous research obtained that oleanolic acid (10) was isolated from Euphorbia paralias (Khafagy et al., 1976), Euphorbia dracunculoides Lam (Chawla et al., 1982), Euphorbia abyssinica Gmel (El-Fiky et al., 2008), Euphorbia chrysocoma (Jiang et al., 2009), and ursolic acid (11) was from E. paralias (Khafagy et al., 1976), E. chrysocoma (Shi et al., 2005), Euphorbia hirta (Mallavadhani and Narasimhan, 2009). The pentacyclic triterpenoids (8–11) described here for the first time in E. kansui. The existence of these triterpenoids may indicate a close relationship with the members of the genus Euphorbia on their chemical composition. Compound 4–6, three diterpenoids, which have not been reported in any other species of Euphorbia, have been shown to be good taxonomic markers for E. kansui. Compound 4 has been previously isolated from E. kansui (Uemura et al., 1974), which can convert to compounds 6 through acetylation of 4-OH. Compounds 5 and 6 have been reported in E. kansui (Uemura et al., 1974) and E. kansui Preparata (Li et al., 2008). The present phytochemical investigation on E. kansui was in a good agreement with other reports. Compounds 1–3, belonging to uncommon C-methylated flavonoids, reported from the family Euphorbiaceae for the first time. Previously these two chalcones and one flavanone were frequently isolated from the families Myrtaceae and Myricaceae (Malterud et al., 1977; Wollenweber et al., 1985; Zhang et al., 1990; Le et al., 1997). It is noteworthy that the occurrence of compounds 1–3 as major components in E. kansui may indicate other similarities in the chemistry of the families Euphorbiaceae, Myrtaceae and Myricaceae. In terms of chemotaxonomy, the compounds 1–6 may sever as the specific makers of E. kansui from Shanxi Province, P. R. China. Acknowledgements This work was financially supported by the Fok Ying Tung Education Foundation (No. 101040) & National Major Special Science and Technology Project (2010ZX09401-304-104A). References Anjaneyulu, A.S.R., Raju, S.N., 1984. Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry 23B, 1010. Anjaneyulu, V., Rao, G.S., 1985. Indian Journal of Pharmaceutical Sciences 47, 194. Chawla, H.M., Chakrabarty, K., Chibber, S.S., Kalia, A.N., Chaudhary, N.C., 1982. Science and Culture 48, 203. Deng, J.Z., Starck, S.R., Hecht, S.M., 1999. Journal of Natural Products 62, 1624. “Dictionary of Chinese Traditional Drugs”, vol. 1, Shanghai Science and Technology Press, Shanghai, 1977, 573. Ding, Y.L., Jia, Z.J., 1992. Phytochemistry 31, 1435. El-Fiky, F., Asres, K., Gibbons, S., Hammoda, H., Badr, J., Umer, S., 2008. Natural Product Communications 3, 1505. Gewali, M.B., Hattori, M., Tezuka, Y., Kikuchi, T., Namba, T., 1990. Phytochemistry 29, 1625. Ikuta, A., Itokawa, H., 1988. Phytochemistry 27, 2813. Jiang, C.Y., Mu, S.Z., Deng, B., Ge, Y.H., Zhang, J.X., Hao, X.J., 2009. Journal of Chinese Medicinal Materials 32, 1390. Khafagy, S.M., Gharbo, S.A., Abdel Salam, N.A., 1976. Planta Medica 29, 301. Le, T.A.D., Nguyen, X.D., Hoang, V.L., 1997. Tap Chi Hoa Hoc 35, 47. Li, C.F., Wang, J.H., Cong, Y., Li, X., 2008. Journal of Asian Natural Products Research 10, 101. Mahato, S.B., Kundu, A.P., 1994. Phytochemistry 37, 1517. Mallavadhani, U.V., Narasimhan, K., 2009. Natural Product Research 23 (7), 644–651. Malterud, K.E., Anthonsen, T., Lorentzen, G.B., 1977. Phytochemistry 16, 1805. Mitscher, L.A., Wu, W.N., Beal, J.L., 1973. Lloydia 36, 422. Shi, H.M., Long, B.S., Cui, X.M., Min, Z.D., 2005. Journal of Asian Natural Products Research 7, 857. Tanaka, R., Matsunaga, S., 1989. Phytochemistry 28, 1699. Uemura, D., Ohwaki, H., Hirata, Y., Chen, Y.P., Hsu, H. Yen, 1974. Tetrahedron Letters 29, 2527. Wang, L.Y., Wang, N.L., Yao, X.S., Miyata, S., Kitanaka, S., 2003. Journal of Natural Products 66, 630. Wollenweber, E., Kohorst, G., Mann, K., Bell, J.M., 1985. Journal of Plant Physiology 117, 423. Zhang, F.X., Liu, M.F., Lu, R.R., 1990. Zhiwu Xuebao 32, 469. Zheng, W.F., Cui, Z., Zhu, Q., 1998. Planta Medica 64, 754.