Malaysian Journal of Analytical Sciences Vol 22 No 1 (2018): 64 - 71

NEW DITERPENOIDS FROM THE ROOTS OF Croton hirtus (EUPHORBIACEAE)

(Diterpenoid-Diterpenoid Terbaharu Daripada Akar Croton hirtus (Euphorbiaceae))

Andi Rifki Rosandy¹, Anis Asmi Azman¹, Rozida Mohd Khalid¹, Rizafizah Othaman¹, Azwan Mat Lazim¹, Iqbal M. Choudary², Yana Maulana Syah³, Jalifah Latip¹, Ikram Md. Said¹, Muntaz Abu Bakar¹*

¹School of Chemical Sciences and Food Technology, Faculty of Science and Technology,

Universiti Kebangsaan Malaysia,43600 UKM Bangi, Selangor, Malaysia

²Hussain Ebrahim Jamal Research Institute of Chemistry,

University of Karachi, Karachi, 75270, Pakistan

³Organic Chemistry Division, Faculty of Mathematics and Natural Sciences,

Institut Teknologi Bandung, Jalan Ganesha 10, Bandung 40132, Indonesia

^*Corresponding author: muntaz@ukm.edu.my

Received: 14 February 2017; Accepted: 28 December 2017

Abstract

The root of Croton hirtus was collected at Tanjung Sepat, Banting for study of its chemical compounds. This sample was dried before being ground and extracted using the methanol solvent at room temperature for three days yielding 18.25 gram of crude extract. The crude extracts obtained were analysed using thin layer chromatography (TLC) then fractionated via vacuum column chromatography (VLC) and proceed the isolation using radial chromatography (RC) to get the pure compounds. The pure compounds obtained were elucidated by nuclear magnetic resonance (NMR), Fourier Transform Infrared (FT-IR) and mass spectroscopy to confirm their structures and from that analysis, the compounds were identified as two new compounds naming (-)-5,8-dihydroxyjatrophan-3-one (1) and (+)-14,16,17-trihydroxykauran-1-on (2) with total weight 4.9 mg and 4.5 mg respectively. This two compound were reported for this time on this genus.

Keywords: Croton hirtus, diterpenoid, euphorbiaceae

Abstrak

Akar Croton hirtus dikumpulkan di Tanjung Sepat, Banting untuk mengkaji sebatian kimianya. Sampel ini dikeringkan sebelum dikisar dan diekstrak dengan menggunakan pelarut metanol pada suhu bilik selama tiga hari dan ia menghasilkan 18.25 g ekstrak mentah. Ekstrak mentah yang diperoleh dianalisis dengan menggunakan kromatografi lapisan nipis (TLC) kemudian difraksikan melalui kromatografi cecair vakum (VLC) dan pengasingan diteruskan dengan menggunakan kromatografi radial (RC) untuk mendapatkan sebatian tulen. Sebatian tulen yang diperoleh ditentukan oleh resonan magnetik nuklear (RMN), inframerah transformasi Fourier (FTIR) dan spektroskopi jisim untuk mengesahkan struktur mereka dan dari analisis itu, sebatian telah dikenal pasti sebagai dua sebatian baru yang diberi nama (-)-5,8- dihidroksijatrophan-3-one (1) dan (+)-14,16,17-trihidroksikauran-1-on (2) dengan jumlah berat masing-masing sebanyak 4.9 mg dan 4.5 mg. Kedua-dua sebatian ini dilaporkan buat kali pertama bagi genus ini.

Kata kunci: Croton hirtus, diterpenoid, euphorbiaceae

References

1. Soernaji, M., Kostermans, A. J. G. H. and Tjittrosoepomo, G. (1976). Weed of rice in Indonesia. Balai Pustaka. Jakarta.

2. Boonyarathanakornkit, L., Che, C., Fong, H. H. S. and Farnsworth, N. R. (1987). Constituents of Croton crassifolius roots. Planta Medica, 54: 61-62.

3. Siems, K., Dominguez, X. A. and Jakupovic, J. (1992). Diterpenes and other constituents from Croton cortesianus. Phytochemistry, 40: 4363-4365.

4. Ngadui, B. T., Abegaz, B. M., Keumedjio, F., Folefoc, G. N. and Kapche, G. W. F. (2002). Diterpenoids from the stem bark of Croton zambesicus. Phytochemistry, 60: 345-349.

5. Aguilar-Guadarrama, A. B. and Rios, M. Y. (2004). Three new sesquiterpenes from Croton arboreous. Journal of Natural Products, 67: 914-917.

6. Chatterjee, A., Banerjee, A. and Bohlman, F. (1977). Crotocaudin: A rearranged labdane type nor-diterpene from Croton caudatus Geisel. Tetrahedron, 33: 2407-2414.

7. Craveiro, A. and Silveira, E. R. (1982). Two cleistanthane type diterpenes from Croton sonderianus. Phytochemistry, 21: 2571-2574.

8. Monte, F. J. R., Dante, E. M. G. and Braz, R. (1988). New diterpenoids from Croton argyarophylloides. Phytochemistry, 27: 3209-3212.

9. Ichihara, Y., Takeya, K., Hitotsuyanagi, Y., Morita, H. and Itokawa, H. (1992). Cajucarinolide and isocajucarinolide: Anti-inflammatory diterpenes from Croton cajucara. Planta Medica, 58: 549-551.

10. Babili, F. E., Moulis, C., Bon, M., Respaud, M. J. and Fouraste, I. (1998). Three furano-diterpenes from the bark of Croton campestris. Phytochemistry, 48: 165-169.

11. Farias, A. C. G., Melo, P. S., Aoyama, H., Haun, M., Duran, N. and Ferreira, C. V. (2002). Cytotoxic effect of the diterpene lactone dehydrocrotonin from Croton cajucara on human promyelocytic leukemia cells. Planta Medica, 69: 67-69.

12. Puebla, P., Correa, S. X., Guerrero, M., Carron, R. and San Feliciano, A. (2005). New cis-clerodane diterpenoids from Croton schiedeanus. Chemical Pharma Bulletin (Tokyo), 53: 328-329.

13. Norizan Ahmat, A. H., Ikram M. S., Jalifah Latip, Laily B. D., Syah Y. M. and Euis H. H. (2007). Styryldehydropyrone and clerodane-type diterpene from Croton argyratus. Malaysian Journal of Analytical Sciences, 11(1): 189-192.

14. Maciel, M. A. (2000). Ethnopharmacology, phytochemistry and pharmacology a successful combination in the study of Croton cajucara. Journal of Ethnnopharmacology, 70: 41-45.

15. Barbosa, P. R., Fascio, M., Martins, D., Maria, L., Guedes, S. and Roque, N. F. (2003). Triterpenes of Croton betulaster (Euphorbiaceae). Biochemical Systematics and Ecology, 31: 307-308.

16. Mulholland, D. A., Langat, M. K., Crouch, N. R., Coley, H. M., Mutambi, E. M. and Nuzillard, J. (2010). Cembranolides from the stem bark of the southern African medicinal plant, Croton gratissimus (Euphorbiaceae). Phytochemistry, 71: 1381–1386.

17. Gelaw, H., Adane, L., Tariku, Y. and Hailu, A. (2012). Isolation of Crotepoxide From Berries of Croton macrostachyus and Evaluation of Its Anti-Leishmanial Activity. Journal of Pharmacognosy and Phytochemistry, 1(4):15-24.

18. Kawakami, S., Matsunami, K., Otsuka, H., Shinzato, T. and Takeda, H. (2011). Crotonionosides A–G: Megastigmane glycosides from leaves of Croton cascarilloides Räuschel. Phytochemistry, 72: 147–153.

19. Fuentes, J. C., Castro, V., Jakupovic, J. and Murillo, R. (2004). Diterpenos y otros constituyentes de Croton hirtus (Euphorbiaceae). Revista de Biología Tropical, 52(1): 269-285.

20. de Lima, S. G., Medeiros, L. B. P., Cunha, C. N. L. C., da Silva, D., de Andrade, N. C., Moita Neto, J. M., Lopes, J. A.D., Steffen, R. A., Araújo, B. Q. and Reis, F. de A. M. (2012). Chemical composition of essential oils of Croton hirtusL’Her from Piauí (Brazil). Journal of Essential oil Research, 24(4): 371-376.

21. Puebla, P., Lopez, J. L., Guerrero, M., Carron, R., Martin, M. L., Roman, L. S. and Feliciano, A. S. (2003). Neo-Clerodane diterpenoids from Croton Schiedeanus. Phytochemistry, 62: 551-555.

22. Barbosa, P. S., Abreu, A. S., Batista, E. F., Guilhon, G. M. S. P., Müller, A. H., Arruda, M. S. P., Santos, L. S., Arruda, A. C. and Secco, R. S. (2007). Glutarimide alkaloids and terpenoids from Croton pullei var. glabrior Lanj. Biochemical Systematics and Ecology, 35: 887-890.

23. Yang, X. D., Chen, W., Zhao, J. F., Yang, L. J., Zhang, H. B., Li, L. (2009). Ent-kaurane diterpenes and phenolic compounds from Croton kongensis (Euphorbiaceae). Biochemical Systematics and Ecology, 37: 237–240.

24. Kupchan, S. M., Sigel, C. W., Matz, M. J., Saenz Renauld, J. A., Haltiwanger, R. C. and Bryan, R.F. (1970). Jatrophone, a novel macrocyclic diterpenoid tumor inhibitor from Jatropha gossypiifolia. Journal of American Chemical Society, 92(14:, 4476-4477.

25. Kupchan, S. M., Sigel, C. W., Matz, M. J., Gilmore, C. J. and Bryan, R. F. (1976). Structure and stereochemistry of jatrophone, a novel macrocyclic diterpenoid tumor inhibitor. Journal of American Chemical Society, 98(8): 2295-2300.

26. Taylor, M. D., Smith, A. B., Furst, G. T., Gunasekara, S. P., Bevelle, C. A., Cordell, G. A., Farnsworth, N. R., Kupchan, S. M., Uchida, H., Branfman, A. R., Daily, R. G. and Sneden, A. T. (1983). Plant anticancer agents. 28. New antileukemic jatrophone derivatives from Jatropha gossypiifolia: structural and stereochemical assignment through nuclear magnetic resonance spectroscopy. Journal of American Chemical Society, 105: 3177-3183.

27. Goulart Marilla, O. F., Sant'Ana, Antonio Euzebio G., De Lima, Roberto A., Cavalcante Sergio, H., De Carvalho, Mario G., Braz Filho and Raimundo .(1993). Fitoconstituintes Químicos Isolados de Jatropha elliptica. Atribuição dos Deslocamentos Químicos dos Átomos de Carbono e Hidrogênio dos Diterpenos Jatrofolonas A e B. Química Nova, 16(2): 95–100.

28. Das, B. and Venkataiah, B. (1999). A rare diterpene from Jatropha gossypiifolia. Biochemical Systematics and Ecology, 27: 759–760.

29. Ravindranath, N., Venkataiah, B., Ramesh, C., Jayaprakash, P. and Das, B. (2003). Jatrophenone, a Novel Macrocyclic Bioactive Diterpene from Jatropha gossypifolia. Chemical and Pharmaceutical Bulletin, 51(7): 870-971.

30. Aiyelaagbe, O. O., Adesogan, E. K., Ekundayo, O. and Gloer, J. B. (2007). Antibacterial diterpenoids from Jatropha podagrica Hook. Phytochemistry, 68: 2420–2425.

31. Pertino, M., Schmeda-Hirschmann, G., Rodríguez, J. A. and Theoduloz, C. (2007). Gastroprotective effect and cytotoxicity of terpenes from the Paraguayan crude drug “yagua rova” (Jatropha isabelli). Journal of Ethnopharmacology, 111: 553-559.

32. Das, B., Laxminarayana, K., Krishnaiah, M., Srinivas, Y. and Raju, T. V. (2009). Multidione, a novel diterpenoid from Jatropha multifida. Tetrahedron Letters, 50: 4885-4887

33. Rédei, D., Forgo, P., Molnár, J., Szabó, P., Zorig, T. and Hohmann, J. (2012). Jatrophane diterpenoids with multidrug resistance-modulating activity from Euphorbia mongolica Prokh. Tetrahedron, 68: 8403-8407.

34. Hegazy, M. E. F., Mohamed, A. E. H., Aoki, N., Ikeuchi, Ohta, E. and Ohta, S. (2010). Bioactive jatrophane diterpenes from Euphorbia guyoniana. Phytochemistry, 71: 249-253.

35. Pešić, M., Banković, J., Aljančić, I. S., Todorović, N. M., Jadranin, M., Vajs, V. E., Tešević, V. V., Vučković, I., Momčilović, M., Marković, I. D., Tanić, N. and Ruždijić, S. (2011). New anti-cancer characteristics of jatrophane diterpenes from Euphorbia dendroides. Food and Chemical Toxicology, 49: 3165–3173.

36. Harinantenaina, L., Kasai, R. and Yamasaki, K. (2002). Ent-kaurane diterpenoid glycosides from a Malagasy endemic plant, Cussonia vantsilana. Phytochemistry, 61: 367–372.

37. Aráoz, M. V. C., Mercado, M. I., Grau, A. and Catalán, C. A. N. (2010). Ent-kaurane derivatives from the root cortex of yacon and other three Smallanthus species (Heliantheae, Asteraceae). Biochemical Systematics and Ecology, 38: 1042–1048.