Molecules 2011, 16, 2785-2795; doi:10.

3390/molecules16042785
OPEN ACCESS

molecules
ISSN 1420-3049 www.mdpi.com/journal/molecules Article

Antifeedant Triterpenoids from the Seeds and Bark of Lansium domesticum cv Kokossan (Meliaceae)
Tri Mayanti 1, Roekmiati Tjokronegoro 1, Unang Supratman 1,*, Mat Ropi Mukhtar 2, Khalijah Awang 2 and A. Hamid A. Hadi 2
1

2

Department of Chemistry, Faculty of Mathematics and Natural Sciences, Padjadjaran University, Jatinangor 45363, Indonesia Department of Chemistry, Faculty of Science, University of Malaya, Kuala Lumpur 50603, Malaysia; E-Mails: matropi@um.edu.my (M.R.M.); khalijah@um.edu.my (K.A.); ahamid@um.edu.my (A.H.A.H.)

* To whom correspondence should be addressed; E-Mail: u_supratman@unpad.ac.id; Tel.: 62-22-7794391; Fax: 62-22-7794391. Received: 31 December 2010; in revised form: 28 February 2011 / Accepted: 2 March 2011 / Published: 29 March 2011

Abstract: Two tetranortriterpenoids, kokosanolide A (1) and C (2) were isolated from the seeds and three onoceranoid-type triterpenoids: kokosanolide B (3), 8,14-secogammacera7,14-diene-3,21-dione (4) and a 1.5:0.5 mixture of 8,14-secogammacera-7,14(27)-diene3,21-dione (5) and compound 4 were isolated from the bark of kokossan (Lansium domesticum). Complete 1H- and 13C-NMR data of the triterpenoids 1-5 are reported. The triterpenoids’ structures were elucidated primarily by means of high field 1D- and 2DNMR, IR and HRMS spectral data. Triterpenoids 1-5 exhibited moderate to strong antifeedant activity against the fourth instar larvae of Epilachna vigintioctopunctata. Keywords: kokosanolides; tetranortriterpenoid; onoceranoid; Lansium domesticum; meliaceae; antifeedant activity

1. Introduction Lansium domesticum cv Kokossan (family Meliaceae) is a higher tree, commonly called “kokosan’’ in Indonesia and widely distributed in Southeast Asian countries [1]. This plant has been reported to

Herein. 3 and 5 were established previously by X-ray diffraction [7-9]. triterpenoid glycosides [6]. Figure 1. domesticum was partitioned between n-hexane and ethyl acetate to give the . with 100% antifeedant activity at 1% concentration. Previous phytochemical studies on L. Structure of compounds 1–5. we report the 1H and 13C NMR data and structural elucidation for these compounds 1–5 isolated from seed and bark extracts of the plant. 25 24 O O O H O H O O O H O OH O O 11 9 8 12 13 18 26 23 17 O 6 H3CO 7 5 10 19 4 21 3 1 2 22 OH O 27 14 H O H3CO 16 15 20 1 20 O 2 O 12 11 1 25 9 10 3 O 21 18 13 26 28 27 HO 29 17 30 14 16 5 7 O 24 23 3 O 4 O 5 2. In addition. the methanol extract of L. the MeOH extract of the bark of L.Molecules 2011. Results and Discussion Liquid-liquid partitioning of the MeOH extract of the seed of L. During the course of our continuing search for novel antifeedant compounds from tropical Meliaceae plants. domesticum cv Kokossan into nhexane. domesticum reported the presence of tetranortriterpenoids [3-5]. The structures of compounds 1. Purification of the n-hexane fraction using silica gel 60 open column chromatography led to the isolation of compounds 1 and 2. domesticum showed strong antifeedant activity against the fourth instar larvae of Epilachna vigintioctopunctata. 16 2786 produce fruits and contain a bitter seed substance with antifeedant activity [2]. EtOAc and aqueous MeOH fractions gave the n-hexane fraction (4 g) as the most active one. onoceranoid-type triterpenoids [1] and onocerandiendione-type triterpenoids [5].

6) and C-14 (δ 168.5 (s) and 110. s) [3.5). including characteristic signals due to a furan ring [δ 143.67) that was ascribed to the C-27 methoxy protons. The signals correlating H-15 (δ 6.46.98.1).40 and 6. supporting the presence of tetranortriterpenoid structure with a furan ring [3-5].and 13C-NMR spectral data (Table 1). 16 2787 ethyl acetate fraction.8 (d)].28) with C-8 (δ 34. Figure 2.6 and 116. The 1H-1H COSY spectrum of 1 showed proton correlations of H5/H6.7). H9/H11/H12.5). and H24/H25. Kokosanolide A (1) was obtained as a white needle-like crystals.28 (1H. which combined with the 1H.17) revealed correlations to C-23 (δ 120.77) with C-1 (δ 108.4 and 165.631 cm−1) and gem-dimethyl (νmax 1.4). . The connectivity of these partial structures were established from the HMBC spectral data (Figure 2). C-13(δ 39. one oxygenated carbon (δ 108. together with APT spectra. The 13 C-NMR.8) and C-26 (δ 141.9 (d). C-9 (δ 69. m. A crude ethyl acetate fraction was subjected to vacuum column chromatography on silica gel 60 and further purified by silica gel column chromatography to yield compounds 3–5. 7. C-2 (δ 76.709 cm−1).753 cm−1). 1. C-24 (δ 110. indicating that the furan ring was located at C-17.6). The UV spectrum showed an absorption maximum at 282 nm (ε 4. The 1H-NMR spectrum showed the presence of three singlets (δ 0.600). 141. a ketone (δ 208.46 and 2. A singlet appeared in the downfield region (δ 3. two ester groups (δ 172.33.4].9). 120.4) and α.37) from tertiary methyl groups and one doublet at δ 1. from n-hexaneEtOAc.43 and the presence of an olefinic signal of an α. and C-16 (δ 165. thus indicated 12 degrees of unsaturation. 25 24 O 23 26 O O H3C O H H 21 20 O 27 7 H3C 6 5 4 21 19 H O 10 3 11 12 13 18 H H3C 6 5 4 3 11 12 18 O 1 H 17 O 1 O 2 9 8 22 13 14 H 17 9 8 H3C O 2 22 14 O O O 16 15 H H 15 16 H H OH O a OH O b O 20 The oxygenated H-17 (δ 5. The positioning of the pyran ring was established by the correlation signals of H-22 (δH 2. Selected HMBC (H→C) (a) and NOESY (↔) (b) correlations of kokosanolide A. a ketone (νmax 1.4). suggested the presence of an α.6).6).5). [M+H]+). H5/H10/H19. isolated double bond (νmax 1.449 and 1.07 and 1.13 (J = 8 Hz) from a secondary methyl group which in turn was correlated to H-10 (δ 3. 178–180 °C. A detailed analysis of 1H-NMR spectrum showed characteristic signals of a tetranortriterpenoid skeleton with a β-substituted furan at δ 7.4).427 cm−1).β-unsaturated ketone (δ 168. H9/H8/H22.p. The IR spectrum showed bands which were ascribable to hydroxyl (νmax 3.β-unsaturated ketone at δ 6. 1H.Molecules 2011.8093. unsaturated ketone (νmax 1. J = 8 Hz). C-8 (δ 34. thus suggesting that 1 possesed a hexacyclic structure with a furan moiety.5 (d).389 cm−1) functionalities.β-unsaturated δ-lactone ring system. indicating the presence of an α-β-unsaturated ketone. revealed 27 carbon signals. q. Its molecular formula was established to be C27H32O9 by LC-ESI-MS data (m/z 500.

3) 2. dd.6 (s) 168. 10 3.7. . 5.9 (q) 25.4 (t) 38.43 (1H.6 (s) 48. 11. 13.98 (3H.9 (t) 47.47 (1H. 13.9 (s) 34.46 (1H. s) 3. 13. m) 1. 5. J Hz) 1.6 (s) 116. dd.8 (d) 141.91 (1H.82 (1H. m) 1. s) 2. a Position 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27-OCH3 C NMR δC (mult. 16 Table 1.2 (d) 142.8) 0. s) 1.70 (1H.5 (d) 26. 23.5. d.7 (t) 119.76 (1H. 5. 21 3.81 (1H.4 (s) 56. 13 9.4 (s) 81.40 (1H.71 (1H.37 (3H.2 (q) 23. s) 3. m) 1.4 (s) 76.77 (1H.74 (1H. 4.6 (d) 69. 7 14 14 2. 8) 1.5) 4. m) 6.29 (1H.8 (s) 55. s) 7. mult.3 (q) 30. d.4) 7.26 (1H.5 (d) 18. NMR spectral data for compounds 1 and 2. 6.4 (s) 81. 5.28 (1H. 26 23.1 (s) 208.33 (1H. 25 - C NMR δC (mult.98 (3H. m) 2. dd.2 (q) 12. 7) 4.4 (d) 77.43 (1H. J Hz) 2.37 (3H.5 (d) 37.12 (1H.31 (1H. s) 1. 17 8.13 (1H.7 (q) 23. 12. s) 7. mult. s) 1 Taken in CDCl3 at 500 MHz for 1H and at 125 MHz for 13C. d.8 (t) 39. m) 1. s) 1 HMBC (1H to 13C) 1.7 (q) 30.1 (q) 25. 4.27 (1H. d.39 (1H.7 (d) 171.. 7.6 (q) 11. d. 9. 2. m) 3. 4. m) 4. 25. 24. s) 5. 26 23. 19 8. m) 1. 16 14. m) 3. s) 1.14 (1H. 4.7) 6.23 (1H.4 (d) 172.4 (s) 117. 8.3 (d) 25.13 (3H.5 (d) 141. 5.2 (q) 13 2 H NMR δH (integral. dd.3.1 (s) 20. 4.41 (1H. 4. 3.8 (d) 143. 5.5 (s) 110.9 (d) 52.6 (q) a 13 2788 1 H NMR δH (integral.2) 2.. dd.79 (1H. m) 1. 4) 2.40 (1H. s) 1. q. 7. 17 1. 14.18 (1H. s) 2.68 (3H.. 20 1.4 (t) 120.90 (1H.45 (1H. 10 4. d.67 (3H.64 (1H. 24. 4.7 (d) 19.8 (t) 29.3 (t) 27.9 (d) 76. 6.4 (d) 52. 6) 4. 4) 2.4 (s) 34. 5. 24.8 (d) 36.4 (d) 165. ppm) 108. 3.17 (1H. 14 23. 3.9 (s) 76. m) 6. m) 1. s) 1. s) 1. 4.7 (s) 110.07 (3H. d. s) 5.7 (d) 165. m) 2.4 (s) 167. ppm) 106.26 (3H. m) 6.72 (1H.47 (1H.17 (3H. 7.4 (d) 67.4) 7. 8) 0.5.Molecules 2011. 26 12..

and 13C-NMR spectral data (Table 2). indicating the presence of an α-β-unsaturated ketone. 1.749. Kokosanolide B (3) was obtained as cubic crystals. one sp2 and four sp3 methines. ORTEP drawing for kokosanolide A reproduced from Mayanti et al. Kokosanolide C (2) was obtained as colorless needle-like crystals from n-hexane-EtOAc and decomposed during the measurement of its melting point.4). The UV spectrum showed an absorption maximum at 275 nm (ε 4.6).Molecules 2011. Correlations between H-6/H-5/H-20 indicated that methyl group and tetrahydrofuran ring should be αorientation. from n-hexane-EtOAc. δH (1H. m. DEPT and the HMQC spectra of 3 revealed the presence of thirty signals: three sp2 and five sp3 quaternary carbons. one sp2 methine (δC 121. The relative configuration of 1 was elucidated by NOESY correlations as shown in Figure 2. suggesting that gem-dimethyl was located at C-4.8 (C-4) and 55. Figure 3.500).4) and C-5 (δH 56. respectively. Among them.704 cm−1). [M+H]+). carbonyl. 1. 1. [7]. 47. a ester carbonyl (νmax 1.9 (C-5). .1 (C-2). 16 2789 Other correlations of methyl signal at δ 0. suggesting that compound 2 was a 3-deoxo derivative of compound 1 and it was thus named kokosanolide C. m) was ascribed to the isolated double bond.72 and 2. The molecular formula of 3 was determined to be C30H48O3 by LC.and 13C-NMR (Table 1) spectra of 2 were quite similar to those of 1.563 cm−1). except for the absence of the ketone signal at δ 208. The IR spectrum showed bands which were ascribable to hydroxyl (νmax 3.41.ESI-MS data (m/z 456. long range correlations were observed between the signals at δ 1. δC 20. C-4 (48.6892. IR absorption bands at 3. and eight methyl groups.p. the gross structure of tetranortriterpenoid 1 was elucidated as a hexacyclic ring system.384 and 1.9].37 to C-3 (δ 208. The 1H. In the HMBC spectrum of 2. The structure and relative stereochemistry were further elucidated by using single-crystal Xray diffraction analysis [7]. Thus.758 cm−1) and unsaturated ketone (νmax 1.5 and appearance of a geminal proton signal at [δH 2.7.18 (1H.and 13C-NMR data. An ORTEP drawing of 1 is shown in Figure 3. NOESY correlation of H-8/H-9 suggesting that pyran ring should be β−orientation.4). The carbomethoxyl signal (δ 3. m). nine sp3 methylenes. Consequently. the structure of tetranortriterpenoid 1 was established to be a tetranortriterpenoid and was named kokosanolide A.71 (1H.18 and the carbon signals at δ 76.98 and 1. and gem-dimethyl functionalities. and combined with the 1H.81) were correlated to an ester carbonyl (δ 172. suggesting that an ester group was located at C-6. 148–150 °C.261 cm−1 suggested the presence of hydroxyl. Analysis of 1H.67) and the signal of H-6 (δ 4. 5. m).705. thus required seven degrees of unsaturation.

whereas H-5 (δ 1.3). The positions of the ketones.23) revealed correlations to carbonyl signal at δ 216. The structure and relative stereochemistry were also elucidated by using single-crystal X-ray diffraction analysis [8]. The methylene signals at C-2 (δ 2. respectively. hydroxyl and isolated double bond were further determined by the COSY and HMBC experiments (Figure 4). Thus. 16 2790 while two carbonyl carbons (δ 216.57) was correlated to C-4 (δ 47.0 ppm. C-21 and C-14. H H 19 11 O 21 H 9 13 8 7 17 H H O 1 H 3 5 HO H H H H 6 Figure 5.1 ppm) and one sp3 carbon (δ 74.42) showed correlations to C-22 (δ 47.6) and C-3 (δ 216.9.46 ) to oxygenated carbon at δC 74. C-9 (δ 55. respectively).14-secogammacera-14-hydroxy-7-ene-3.6 ) and C-21 (δ 217. whereas the methine signal at C-17 (δ 1.26) showed correlations to the carbonyl signal at δ 217. Selected HMBC (H→ C) and COSY ( ) correlations for kokosanolide B.5) and C-8 (δ 135.0 ppm and correlation between methylene signals at C-15 (δC 1. H-7 (δ 5. An oxygenated tertiary carbon signal was revealed to be C-14 by the correlation between methine signal at C-13 (δC 1.21-dione and was named kokosanolide B. [8]. the methylene signals at C-20 (δ 2. thus suggesting the other carbonyl group and gem-dimethyls were located at C-21 and C-22.0) were assigned to those bearing an oxygen atom (C-3. ORTEP drawing for kokosanolide B reproduced from Supratman et al.9). indicating that one of the carbonyl moeity and gem-dimethyl are placed at C-3 and C-4. . suggesting that an isolated double bond is located at C-7 and C-8.Molecules 2011. Furthermore.9 and 217.1).12 ) to oxygenated carbon at δC 74.41) showed correlations to C-6 (δ 28. An ORTEP drawing of 3 is shown in Figure 5. suggesting that compound 3 was an onoceranoid-type triterpenoid [5].1. Figure 4. the structure of onoceranoidtype triterpenoid 3 was determined as 8. respectively.9).

10 (1H.23 (1H.3 (q) 24. m) 1.72 (3H.1 (q) 21.5 (q) 25. s) 1. m).84 (1H.09 (3H.65 (1H. 5. m).04 (3H. 10). 1.6 (d) 28. 2..59 (1H.61 (1H. m) 1.93 (1H.40 (1H.Molecules 2011. NMR spectral data for compound 3 and 4. m) 1. 24 23 5. m) 1. 2.41 (1H. m) 1.6 (s) 51.77 (3H. 1.56 (1H. J Hz) 1.41 (1H.41 (1H. 17 17 18. 10) 1.5 (d) 36.6 (d) 135. 10 8 26 9 9 17 14.93 (3H. 2.7 (d) 135. m) 2. . 2. 29 C NMR δC (mult. dd.6 (s) 25. 2. m).23 (1H.78 (1H. 10 3 9.6 (d) 30. 5. 21 5.1 (d) 30. m) 1. s) 1. m) 1. m) 2. m) 1. 10). m) 1.24 (1H.1 (d) 135. m) 2. 22.70 (1H. 30 17. 3.9 (s) 47. m) 5.5 (t) 21. 15 13. 5. dd.1 (t) 122. m).4 (t) 55. 2. s) 1. 2. m) 1. J Hz) 1. 14. m) 5. m).73 (1H.09 (1H.6 (d) 36.43 (1H.57 (1H. m). mult. 1. 7) 1.62 (1H.3 (q) 13. mult.1 (t) 51. 7) 1. 1. m) 1. 5.8 (t) 216.0 (s) 44. 10. s) 0.4 (q) 22. ppm) 38. m). s) 1.12 (1H. s) 1. s) 0.3 (q) 13 4 H NMR δH (integral. 22 21 19.. s) 1 HMBC (1H to 13C) 2.6 (s) 21. s) 0. m). 10) 5.65 (1H. s) 1 a Taken in CDCl3 at 500 MHz for 1H and at 125 MHz for 13C. m). 16 Table 2.2 (t) 31.12 (1H.3 (s) 55. dd.24 (1H. 7.6 (s) 38.1 (s) 47.33 (1H.21 (3H. 2.8 (t) 216. dd.91 (1H. m).5 (q) 22.97 (3H. s) 1.5 (t) 34.5 (q) 13 2791 3 H NMR δH (integral. m). m).09 (1H.9 (s) 47.5 (q) 13. 17 17. m) 1. m) 1. 2. m) 1.1 (q) 22.2 (t) 55.4 (t) 34. m).04 (3H. s) 0.76 (1H. 9.7 (s) 24.33 (1H. ppm) 38.5 (t) 34. 10 9 13. 2. 2.6 (s) 25.9 (t) 121. s) 1.43 (1H.5 (t) 61.9 (s) 47. s) 1.46 (1H.26 (1H.97 (3H.4 (q) 26..59 (1H.70 (1H. dd.8 (t) 216.02 (3H.04 (3H. a Position 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 C NMR δC (mult.2 (q) 15.08 (3H. m).46 (1H.1 (q) 22.72 (3H. 24 7.8 (d) 74.2 (d) 36.24 (1H.24 (1H.3 (s) 122. m) 1..7 (s) 38. 2.09 (3H. s) 1.1 (t) 217. m) 1.08 (1H.96 (3H. dd.6 (s) 51.09 (3H.3 (s) 55.40 (1H.42 (1H.5 (q) 22. s) 1.6 (d) 36. m) 2.51 (1H.3 (q) 13. 2. m).59 (1H.1 (q) 22.46 (1H. 7.2 (t) 24.93 (1H. m) 1. m) 1.5 (t) 34.

except for the appearance of methylene protons and an sp2 carbon at C-27 [δH 5. The signal of olefinic proton H-15 (δ 5.6) and C-16 (δ 30. [9]. compound 4 was identified as a 8.21-dione [5]. thus.1 and 135. ORTEP drawing for 5 reproduced from Tjokronegero et al. kokosanolide C (2). [M+H]+).360 cm−1). similar to those of kokosanolide B.Molecules 2011.45 (1H. m). which together with 1H.14-secogammacera-7. 143–144 °C. Compound 4 showed no absorption maxima in the UV spectrum indicating the absence of a conjugated double bond.5 Hz).1).14-diene-3.5. The 13C-NMR spectrum of 4 showed 15 signals. The essential differences between the NMR spectra of 4 and kokosanolide B consisted of the absence of a hydroxyl group and appearance of a double bond [δ 5.43) was correlated to C-14 (δ 135. suggesting that 4 has two similar unit structure.p. The antifeedant activities of compounds 1–5 are shown in Table 3. C-13 (δ 55. J = 10. requires eight degrees of unsaturation. m.662 cm−1) and gem-dimethyl (νmax 1. HMBC experiments were carried out.430 and 1.708 cm−1). whereas 8. It was isolated together with compound 4 with a ratio of 1.14-diene-3. suggesting that 4 was a dehydroxy derivative of kokosanolide B.12 (1H. The IR spectrum showed bands which were ascribed to a ketone (νmax 1.43 (1H. The structure was elucidated by using a single-crystal X-ray diffraction analysis [9] and the ORTEP drawing for 5 is shown in Figure 6 below. suggesting that 4 has a symmetrical structure.5:0. The molecular formula of 4 was determined to be C30H46O2 by LC-ESI-MS data (m/z 438. indicating that 5 is an isomer of 4.3745. J = 10. lacking the ketone group.14-secogammacera-14-hydroxy-7-ene-3. δH 122.2-dione (4) was obtained as a white needle-like crystals.5 Hz). Compound (5) was identified as 8. In order to determine the connectivity of the partial structure due to a newly double bond.3] and fifteen carbon signals. δC 122.14(27)-diene-3.and 13C-NMR spectral data (Table 2).3).21-dione (3) having the hydroxyl group showed the strongest activity. Among those compounds. Figure 6. 16 2792 8. isolated double bond (νmax 1. 5. from n-hexane-EtOAc.14-Secogammacera-7. The 1H and 13C-NMR spectra of 5 were similar to those of 4.14-secogammacera-7. suggested that an oxygenated fuctional group was an important structural component for antifeedant activity. showed less antifeedant potency. indicating that a new double bond was located at C-14 and C-15. .1]. Consequently. Compounds 1–5 were evaluated for antifeedant activity against the fourth instar larvae of Epilachna vigintioctopunctata at a concentration of 1%.21-dione.

0. Antifeedant bioassay Compounds 1–5 at a concentration of 1% were subjected to select antifeedant assays on Solanum nigrum leaves against 4th instars larvae of Epilachna vigintioctopunctata. The plant was identified by the staff of the Laboratory of Plant Taxonomy. Department of Biology. All ORTEP diagrams were obtained from previous reports.14-diene-3.2. Padjadjaran University.14-Secogammacera-7. Extraction and isolation Dried seeds of L. The fraction eluted with n-hexane-dichloromethane (6:4) was further separated by column chromatography on silica gel (n-hexane-ethyl acetate 7:3) to give 1 (150 mg) and 2 (26 mg). The n-hexane extract was subjected to column chromatography on silica gel 60 using a n-hexane and dichloromethane (8:2).21-dione (5) 3.14-Secogammacera-7.14(27)-diene-3.5 L) and 10% aqueous methanol (2.Molecules 2011. domesticum cv kokossan (2 kg) were extracted exhaustively with methanol 12 L at room temperature for 3 days. The mass spectra were recorded with a Mariner Biospectrometry-Finnigan instrument. 1 H. 10184) was deposited at the herbarium of the Padjadjaran University. A voucher specimen (No.21-dione (4) 8. General Activity (%) 78 0 99 85 56 2793 Melting points were measured on an Electrothermal melting point apparatus and are uncorrected. Experimental 3. 3. Bandung. The resulting methanol extract (84 g) was partitioned between nhexane (2. Indonesia in March 2006. Antifeedant activity (%AF) was determined by using the equation %AF = (1 – treatment consumption/control consumption) × 100 [11]. West Java Province.25 mm) and detection was achieved by spraying with 10% H2SO4 in ethanol. 3. TLC plates were precoated with silica GF254 (Merck. The antifeedant activities of 1–5 at 1% concentration are presented in Table 3. Optical rotations were recorded on a Perkin-Elmer 341 polarimeter. Compound Kokosanolide A (1) Kokosanolide C (2) Kokosanolide B (3) 8. The UV spectra were obtained on a UV Ultraspec 3000 Pro spectrophotometer. Chromatographic separations were carried out on silica gel 60 (Merck). domesticum cv Kokossan were collected in Cililin District. .5 L) to give an n-hexane soluble fraction (4 g) after removal of the solvent. Indonesia. followed by heating. Antifeedant activity of compounds 1–5.3.4.1. 16 Table 3. Plant material The bark and seed of L.and 13C-NMR spectra were obtained with a JEOL JNM A-500 spectrometer using TMS as internal standard. The IR spectra were recorded on a Perkin-Elmer 1760X FT-IR in KBr. 3.

see Table 1. . 7 Hz). 1. 1. 5. 1.95 (3H. δC (ppm).389 cm−1. J = 10. s).5. 2.454 and 1. 1.631.261 cm−1. 47. CHCl3).14-Secogammacera-7.708. 22. dd.5 g).65 (1H.79 (1H. 1. 16 2794 The dried bark of L.10 (3H. 1. Colorless needle-like crystals. see Table 1.749. 125 MHz). m). MeOH).2. The active fraction was further chromatographed on silica gel using nhexane/acetone (90:10) to give 3 (10 mg). s).70 (1H.15 (1H. 2. m).3745.40 (1H. 1. 8. dd. J = 7. m). IR (KBr) νmax 3. s). 125 MHz). 1.63 (1H. 4.14(27)-diene-3. 13C-NMR (CDCl3.0.3. 22. 36. 1. 8. The fraction eluted with n-hexane:ethyl acetate (80:20) was further separated by column chromatography on silica gel using n-hexane:ethyl acetate (95:5) to yield an active fraction (1. 1. m). s). 500 MHz).04 (1H. 0. 500 MHz).563 cm−1. 13. 125 MHz). 5.21-dione (4).93 (1H. Kokosanolide C (2). 1. m). 1.5. 13C-NMR (CDCl3. 500 MHz). m). MeOH).3. s). m). cubic crystals. 500 MHz).758 cm−1. CHCl3). m). 34.5 Hz).35 (1H. kokosanolide B.09 (1H.384 and 1. IR (KBr) νmax 3. 217. LC-ESI-MS data (m/z 456. 1.9. m). 51.9. LC-ESI-MS data (m/z 500. 25. domesticum cv kokossan (3 kg) was extracted exhaustively with methanol 15 L at room temperature for 3 days. 10 Hz). s). Conclusions The methanolic extract from the dried seed and bark of Lansium domesticum cv kokossan yield two tetranortriterpenoids – kokosanolide A and C – and one onoceranoid-type triterpenoid.449 and 1. 34.04 (3H. 135.5.43 (1H.5. IR (KBr) νmax 1. 500 MHz). 1. m).14-diene-3.14-secogammacera-7. along with two onoceranoid-type triterpenoids. This study also suggests that the Lansium plants contain potent antifeedant compounds for further application. UV (λmax in EtOH) 282 nm (ε 4.360 cm−1. 17. 125 MHz).7. [M+H]+). 1.14-diene-3.5). Kokosanolide B (3).709. m). J = 10. [M+H]+). 1H-NMR (CDCl3. 1.1. 1. m).5 Hz). m).09 (3H.45 (1H. LC-ESI-MS data (m/z438. 30.667. IR (KBr) νmax 1.Molecules 2011. see Table 1. The results of this study provide a basis for futher phytochemical studies on the Lansium plants. 1. [α]20D – 18. Kokosanolide A (1). 2. 122. 2.08 (3H.427. 1. 1. 13C-NMR (CDCl3. 0.753. m).21-dione and a mixture of 8.1.8093.46 (1H. m). Needle-like crystals. 51. 13C-NMR (CDCl3.24 (1H. The ethyl acetate fraction was subjected to vacuum column chromatography on silica gel 60 by using a step gradient of n-hexane/ethyl acetate. 1.6. 2. s). 2.6.22 (3H. 10 Hz). s).45 (1H. 1. 13C-NMR (CDCl3. The methanol extract (250 g) was partitioned with n-hexane (3 L) and ethyl acetate (3 L) to give an n-hexane soluble fraction (70 g) and an ethyl acetate soluble fraction (40 g).384 cm−1. see Table 2. 1. IR (KBr) νmax 3. [α]20D + 85° (c 0. see Table 2.20 (1H. [α]20D − 8° (c 0.21-dione and 8.705.14(27)-diene-3. dd.600). 1. δH (ppm). [α]20D + 96° (c 0.430.14-Secogammacera-7. see Table 1.2.83 (1H. 216. 1H-NMR (CDCl3. 38.50 (1H.21-dione (5). 125 MHz). see Table 2. White needle-like crystals.14-diene-3.40 (1H. 24. UV (λmax in EtOH) 275 nm (ε 4. 1.6892. 5.72 (3H.5:0.21dione (1. 1H-NMR (CDCl3.1.5.97 (3H. 1. 8.24 (1H.500).04 cm−1. 2.33 (1H. m).0. 1H-NMR (CDCl3. 2.5. 1. 4 (50 mg) and 5 (24 mg). J = 5.14-secogammacera-7.8. [M+H]+).662. 1H-NMR (CDCl3. J = 5. m).5° (c 01.59 (1H. 1. 1.14-secogammacera-7. m).6. Needle-like crystals. 55.12 (1H. see Table 2.

Fields. Nishide. M.. Indonesia and I-MHERE project of Padjadjaran University for financial support. 23. J. 2010.. J.. Indonesian Science Institute. 1982.. 1985. Ng. Y. 2002. Org.14-diene-3. J. S. M. Ehhammer... Kowithayakorn. Stored Prod.G... B.. Nat. Komiyama. Koyana. Durst. Y.W. Kinnon. Saewan.D. 9. 5.. Shiro. M.. Supratman. E65. o1448.. 50. Shiro. S.14(27)-diene-3. References Omar.. Acta Cryst.... © 2011 by the authors. U. K.Molecules 2011.. licensee MDPI. for NMR and LC-ESI-MS measurements.21-dione (1. 67. M. Arnason.B. Chantrapromma. Zhang.. T. o750. Mayanti. Antimalarial tetranorterpenoids from the seeds of Lansium domesticum Corr. E. o1621. 2009. New onoceranoid triterpene constituents from Lansium domesticum.R. Philogene.. Leaman. Phytochemistry 2006. Kuala Lumpur. We thank Mr.. 4. M. Kokosanolide from the seed of Lansium domesticum Corr. Kenya. Basel.E. Ahmad Darmawan and Mrs. D. 2009. U. P. Awang. T.. Sastrapradja.. 10. G. Okuyama.N. Structure of Dukonolides. Towers. 8. E65. Y.. M. Tanaka. Awang. K. Supratman. In Proceedings of 3rd International Neem Conference. K... . J. Nishizawa.. Sanchez. 2. Acta Cryst. M... M. Mukhtar. Ng...   Sample Availability: Samples of the compounds 1–5 are available from the authors..R. Biological Activity of Limonoids from the Rutales. Res. Prod. Hayashi. Ministry of National Education. Matta. J.. Malaysia for X-ray measurement.. S. K. M.14secogammacera-7-ene-3. M. 10 July 1986. 3.R. 14-Hydroxy-8. Switzerland. Hayashi. P. Methodology of the Epilachna Varivestis Bioassay of Antifeedants Demonstarted with Some Compounds from Azadirachta indica and Melia azedarach. 1349-1350. 2007. S. Schwinger. Ishibashi. 377-394. 2288-2293. Supratman. 43.. Hayashi.. 16 Acknowledgments 2795 We are grateful to the Directorate General of Higher Education. Mukhtar. University of Malaya. Nairobi. M.E. Nademoto. Chem. 27. Phytochemistry 1992. Phytochemistry 1988. M.5/0.. 6.. 31. 1.W. Acta Cryst. the structure of lansioside A: A novel triterpenes glycoside with amino-sugar from Lansium domesticum. U. Nademoto. T.. Koul.14-secogammacera-7.. S.21-dione from the bark of Lansium domesticum Corr.org/licenses/by/3. Faculty of Science. T.R. Sutherland. Marcotte. S. Bitter Principles of Lansium domesticum.E. 237-239. Tjokronegoro. New tetranortriterpenoid from the seeds of Lansium domesticum. Tetrahedron Lett.. 8.. Mayanti. J..21-dione-8. Y. R. Sofa Fajriah in the Research Center for Chemistry. Isman. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution license (http://creativecommons. Champagne.. T.5) from the bark of Lansium domesticum Corr. R. W. M.. Jimenez. T. H..W. Ng. 1709-1711. Nishizawa. Fujimoto. Mayanti... N.. We are grateful to Ng Seik Weng at Department of Chemistry. Hayashi. D. 5487-5490. Nishizawa. H. 65. 7. M. G. L. 92-96. A. Kraus.0/). Y.H. Poveda. Sastrapradja. E66. 11. O..14-Secogammacera7.T. J. Mukhtar. Scudder. T. Antifeedant activities of triterpenoids isolated from tropical Rutales.

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