Our detailed study on the chemical constituents of the stem bark of Calophyllum benjaminum and Calophyllum javanicum has resulted in one new coumarin benjaminin (1), five xanthones fuscaxanthone C (2), β-mangostin (3), thwaitesixanthone (4), dombakinaxanthone (5) and caloxanthone A (6), together with four common triterpenes friedelin (7), β-sitosterol (8), lupeol (9) and stigmasterol (10). The structures of these compounds were elucidated using NMR, FTIR and GCMS

Daud, Shaari

Ee, Gwendoline Cheng Lian

Mahaiyiddin, A. G.

Muhamad Sahimi, Muhamad Syarik

See, Irene

Sukari, Mohd Aspollah

Teh, Soek Sin

Universiti Putra Malaysia Institutional Repository

Pertanika J. Trop. Agric. Sci. 38 (1): 1 - 6 (2015)ISSN: 1511-3701    © Universiti Putra Malaysia PressTROPICAL AGRICULTURAL SCIENCEJournal homepage: http://www.pertanika.upm.edu.my/Article history:Received: 13 November 2013Accepted: 4 April 2014ARTICLE INFOE-mail addresses: mohdsyariq@gmail.com (Sahimi, M. S. M.),  gwen@upm.edu.my (Ee, G. C. L.),  azeeza90@yahoo.com (Mahaiyiddin, A. G.),  shaari11145@gmail.com (Daud, S.),  judith_teh@hotmail.com (Teh, S. S.),  irenesee88@hotmail.com (See, I.),  aspollah@upm.edu.my (Sukari, M. A.)* Corresponding authorShort CommunicationA New Natural Product Compound Benjaminin from Calophyllum benjaminumSahimi, M. S. M., Ee, G. C. L.*, Mahaiyiddin, A. G., Daud, S., Teh, S. S., See, I. and Sukari, M. A.Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 Serdang, Selangor, MalaysiaABSTRACTOur detailed study on the chemical constituents of the stem bark of Calophyllum benjaminum and Calophyllum javanicum has resulted in one new coumarin benjaminin (1), five xanthones fuscaxanthone C (2), β-mangostin (3), thwaitesixanthone (4), dombakinaxanthone (5) and caloxanthone A (6), together with four common triterpenes friedelin (7), β-sitosterol (8), lupeol (9) and stigmasterol (10). The structures of these compounds were elucidated using NMR, FTIR and GCMS.Keywords: Benjaminin, Calophyllum benjaminum, Calophyllum javanicum, Clusiaceae, coumarin, xanthoneand Calophyllum javanicum are among the many Calophyllum  species that grow in Malaysia. Some Calophyllum species are used in folk medicine to treat rheumatism, wound and inflammation. Previous studies have indicated this genus as rich in secondary metabolites such as xanthones (Morel et al. 2000), coumarins (Ee et al. 2011), and chromanone acids (Cottiglia et al. 2004). Some of the compounds isolated from Calophyllum species exhibited significant biological effects such as cytotoxic activities (Guilet et al. 2001), anti-human immunodeficiency virus (HIV), antimicrobial (Yimdjo et al. 2004) and anti-INTRODUCTIONCalophyllum genus is one of the many genera of the Guttiferae family. This particular genus comprises more than 180 species that are widely distributed in Southeast Asia. Calophyllum benjaminum Sahimi, M. S. M., Ee, G. C. L., Mahaiyiddin, A. G., Daud, S., Teh, S. S., See, I. and Sukari, M. A.2 Pertanika J. Trop. Agric. Sci. 38 (1) 51 - 6 (2015)tumour promoter activities (Itoigawa et al. 2001). As part of our ongoing research on Calophyllum species from Malaysia, we reported here the first phytochemical study on Calophyllum benjaminum and Calophyllum javanicum.MATERIALS AND METHODSExtraction and IsolationThe ground stem bark of both plants was extracted with a series of solvents in increasing polarity, starting with hexane, followed by chloroform, ethyl acetate and methanol respectively for three days for each solvent. The extracts were evaporated to dryness using a rotary vacuum evaporator and the dry extract purified and isolated using column chromatography (Merck silica gel). Eluting solvents, which were of increasing polarity, ranged from 100% hexane to mixtures of hexane and chloroform, mixtures of chloroform and ethyl acetate, ethyl acetate with methanol and 100% methanol. Repeated purifications of the chloroform extract of Calophyllum benjaminum gave benjaminin (1) (11mg) together with fuscaxanthone C (2) (9mg). Meanwhile, β – mangostin (3) (5mg) and calaxanthone A (6) (10mg) were obtained from the methanol extract. The chloroform extract of Calophyllum javanicum gave dombakinaxantone (5) (7mg) and thwaitesixanthone (4) (8mg). Meanwhile, the 1H and 13C NMR spectral data for compounds 2 - 6 (see Fig.2) are in agreement with the data given in the literature (Ito et al., 2003; Mahabusarakam et al., 1987; Iinuma et al., 1994; Ranjith et al., 1997; Dahanayake et al., 1974).Benjaminin (1): Yellowish Oil; FTIR: 3296,2930, 1706, 1621 cm-11H-NMR(CDCl3, 400MHz): d 12.28 (7-OH, s), 5.19 (1H, t, J = 6.29 Hz, H-2″), 4.13 (1H, m, H-3″′), 3.72 (3H, s, 5-OCH3), 3.51 (1H, m, H-4), 3.25 (2H, m, H-1″), 2.74 (2H, d, J = 6.85 Hz, H-3), 2.53 (1H, m, H-2″′), 1.74 (3H, s, H-5″), 1.70 (2H, m, H-1′), 1.67 (3H, s, H-4″), 1.49 (3H, d, J = 6.87, H-CH3-3″′), 1.24 (2H, m, H-3′), 1.22 (2H, m, H-4′), 1.19 (3H, d, J = 6.87 Hz, H- CH3-2″′), 1.11 (2H, m, H-2′), 0.82 (3H, t, J = 6.87, H-5′). 13C-NMR (CDCl3, 100MHz): d 200.42 (C-1″′), 179.27 (C-2), 164.96 (C-5), 160.17 (C-7), 158.60 (C-8a), 131.80 (C-3″), 122.90 (C-2″), 115.26 (C-6), 115.19 (C-4a), 78.76 (C-3″′), 61.92 (OCH3), 46.21 (C-2″′), 39.20 (C-3), 33.87 (C-1′), 32.67 (C-4), 31.95 (C-3′), 27.78 (C-2′), 25.80 (C-4″), 22.68 (C-1″), 22.64 (C-4′), 19.69 (C-CH3-3″′), 17.99 (C-5″), 14.15 (C-5′), 10.34 (C-CH3-4″′)RESULTS AND DISCUSSIONBenjaminin (1) was obtained from the chloroform extract of Calophyllum benjaminum  as a yellowish oil with molecular formula C25H36O6. The EIMS spectrum gave a molecular ion peak at m/z 432. The FTIR spectrum of benjaminin displayed absorbtion peaks at 3296, 2925, 1705, 1626 cm-1, while the UV spectrum gave a maximum absorbtion at 400nm.The 1H NMR signals were assigned through their COSY and HMBC correlations. The 1H-NMR spectrum gave one singlet signal at δ 12.28 implying a hydroxyl peak. One olefinic proton signal at δ 5.19 (t, 1H, Benjaminin from Calophyllum benjaminum 3Pertanika J. Trop. Agric. Sci. 38 (1): 51 - 6 (2015)J = 6.30 Hz), three methine signals at δ 2.53 (m, 1H), 3.51 (m, 1H), and 4.13 (m, 1H) and six methylene signals at δ 1.70 (m, 2H), 1.11 (m, 2H), 1.24 (m, 2H), 1.22 (m, 2H), 3.25 (m, 2H) and 2.74 (d, 2H, J = 6.87 Hz) were also observed. The olefinic signal was assigned to the olefinic (H-2″) proton of the prenyl side chain at C-6 while the methylene signals belong to the four methylene protons of the n-pentyl side chain at C-4 (H-1′, H-2′, H-3′ and H-4′) and the prenyl group (H-1″) and H-3, respectively. Five methyl signals at 0.82 (t, 3H, J = 6.87 Hz, 5′-CH3), 1.74 (s, 3H, 5″-CH3), 1.67 (s, 3H, 4″-CH3), 1.19 (d, 3H, J = 6.87 Hz, 2″′-CH3) and 1.49 (d, 3H, J = 6.87 Hz, 3″′-CH3) were duly assigned to the five methyl groups of the side chains at C-4, C-6 and C-8. One methoxyl group at δ 3.72 (s, 3H) was seen to be attached to C-5 through their 3J correlation in the HMBC spectrum. The 13C-NMR spectrum gave 25 signals and from the analysis of the DEPT experiment, it was concluded that the molecule had five methine carbons, six methylenes, and six methyls plus nine quaternary carbons including the two carbonyl carbons at δ 179.27 and 200.42.The complete elucidation of the structure was achieved with the aid of the HMBC analysis (Fig.1) after assigning the protons to their direct bonding carbons by the HMQC spectrum. The attachment of the n-pentyl group to C-4 was justified by the 2J correlation between H-4 and C-1′. H-1″of the prenyl group was seen to have a cross peak with C-6 (2J) and a 3J correlation with C-7 and C-5. Hence, the attachment of this prenyl side chain to C-6 is obvious. C-7 was concluded to be bonded to an OH group from its 3J correlations with C-8 and C-6 and its 2J correlation with C-7. The methoxyl protons correlated to C-5 via a 3J correlation hence proving its attachment. The doublet signal at δ 2.74, which integrated for 6788a4a5O234O1'2'1''2''3''4''5''HO1'''2'''3'''5"'HO 4"'O3'4'5'OCH3(1)Fig.1: HMBC correlations in benjaminin (1)Sahimi, M. S. M., Ee, G. C. L., Mahaiyiddin, A. G., Daud, S., Teh, S. S., See, I. and Sukari, M. A.4 Pertanika J. Trop. Agric. Sci. 38 (1) 51 - 6 (2015)6785a4a5O234O1'2'1''2''3''4''5''HO1'''2'''3'''HOO3'4'5'OCH3(1)OOH3COH3COOCH3OH(2)OO OHH3COHO OCH3(3)OO OHOO(4)OO OHOHO(5)OOOH OOHOH(6)Fig.2: Structures of compounds 1-6Benjaminin from Calophyllum benjaminum 5Pertanika J. Trop. Agric. Sci. 38 (1): 51 - 6 (2015)2 protons and correlated to C-2 and C-4 via 2J correlations and to C-4a via a 3J correlation, indicated C-3 to be a methylene carbon. The HMBC correlation of the methoxyl proton at δ 3.72 with δ 164.96 (C-5) confirmed its attachment at C-5. Hence, the remaining carbon, which is C-8, could be shown to be attached to a 3-hydroxy-2-methylbutanoyl moiety via HMBC correlations (see Fig.1). The C-2″′proton gave cross peaks with the C-2″′ methyl and C-3″′ methyl groups thus justifying its location. Meanwhile, a HMBC correlation was observed between the C-3″′ methine proton and the carbonyl carbon at position C-1″′. Thus, compound 1 was deduced to be benjaminin with the IUPAC name 7-hydroxy -8-(3-hydroxy-2-methylbutanoyl)-5-methoxy-6-(3-methylbut-2-enyl)-4-pentylchroman-2-one.CONCLUSIONThe detailed isolation work on the stem bark of Calophyllum benjaminum and Calophyllum javanicum have resulted in one new coumarin benjaminin (1), five xanthones fuscaxanthone C (2), β-mangostin (3), thwaitesixanthone (4), dombakinaxanthone (5), and caloxanthone A (6), together with four common triterpenes friedelin (7), β-sitosterol (8), lupeol (9) and stigmasterol (10). There was no report available on this particular plant before.ACKNOWLEDGEMENTSThe UPM Graduate Research Fellowship and the Malaysian Agri Science Fund research grant are gratefully acknowledged.REFERENCESCottiglia, F., Dhanapal, B., Sticher, O., & Heilmann, J. (2004).  New Chromanone Acids with Antibacterial Activity from Calophyllum brasiliense. Journal of Natural Product, 67, 537-541.Dahanayake, M., Kitagawa, l., Sornanathan, R., & Sultanbawa, U. M. S. (1974). Chemical Investigation of Ceylonese Plants, Part V1I. l. Extractives of Calophyllum thwaitesii Planch and Triana and Calophyllurn walkerri Wight (Guttiferae). Journal of the Chemical Society, Perkin Transactions 1, 2510 – 2514.Ee, G. C. L., Mah, S. H., Teh, S. S., Rahmani, M., Go, R., & Taufiq-Yap, Y. H. (2011). Soulamarin, a New Coumarin from Stem Bark of Calophyllum soulattri. Molecules, 13(10), 956-960.Guilet, D., Se´raphin, D., Rondeau, D., Richomme, P., & Bruneton, J. (2001). Cytotoxic coumarins from Calophyllum dispar. Phytochemistry, 58, 571–575.Iinuma, M., Tow, H., Tanaka, T. and Yonemori, S. (1994). Two Xanthones From RootBark of Calophyllum Inophyllum. Phytochemistry, 35, 527-532.Ito, C., Itoigawa, M., Takakura, T., Ruangrungsi, N., Enjo, F., Tokuda, H., Nishino, H., & Furukawa, H. (2003). Chemical Constituents of Garcinia fusca: Structure Elucidation of Eight New Xanthones and Their Cancer Chemopreventive Activity. Journal of Natural Product, 66, 200-205.Sahimi, M. S. M., Ee, G. C. L., Mahaiyiddin, A. G., Daud, S., Teh, S. S., See, I. and Sukari, M. A.6 Pertanika J. Trop. Agric. Sci. 38 (1) 51 - 6 (2015)Itoigawa, M., Ito, C., Tan, H. T.W., Kuchide, M., Tokuda, H., Nishino, H., Furukawa, H. (2001). Cancer chemopreventive agents, 4-phenylcoumarins  f rom Calophyl lum inophyllum. Cancer Letters, 169, 15-19.Mahabusarakam, W. & Wiriyachitra, P. (1987). Chemical Constituents of Garcinia mangostana. Journal of Natural Product, 50, 474-478.Morel, C., Se´raphin D., Oger, J-M., Litaudon, M., Se´venet, T., Richomme, P., & Bruneton J. (2000). New Xanthones from Calophyllum Caledonicum. Journal of Natural Product, 63, 1471-1474.Ranjith, H., Dharmaratne, W., Nishanthi, W. M., & Wuesinghe M. (1997). A Trioxygenated Dipreny la ted  Chromenxanthone  f rom Calophyllum Moonii. Phytochemistry, 46, 1293-1295.Yimdjo, M. C., Azebaze, A. G., Nkengfack, A. E., Meyer, A. M., Bodo, B. and Fomum, Z. T. (2004). Antimicrobial and cytotoxic agents from Calophyllum inophyllum. Phytochemistry, 65, 2789–2795.

A new natural product compound benjaminin from

Calophyllum benjaminum

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A new natural product compound benjaminin from Calophyllum benjaminum

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