Abstract
Molasses of tangerine orange (Citrus unshiu Markovich) is obtained as a waste product in the course of tangerine orange juice production. This molasses is expected to be a useful source of organic compounds such as flavonoids and limonoids. To elucidate a use for this molasses waste, we isolated and identified its organic constituents. Two new flavanonol glycosides were isolated from tangerine orange molasses, along with several flavonoids such as hesperidine, narirutin, eriodictyol, 3′,4′,5,6,7,8-hexamethoxy-3-O-β-d-glucopyranosyloxyflavone, and 3′,4′,5,6,7,8-hexamethoxy- 3-β-d-[4-O-(3-hydroxy-3-methylglutaloyl)]-glucopyranosyloxyflavone, and limonoids such as limonin, nomilin, and cyclic peptide, citrusin III. The structures of the new flavanonol glycosides were determined as (2R,3R)-7-O-(6-O-α-l-rahmnopyranosyl-β-d-glucopyranosyl)-aromadendrin and 7-O-(6-O-α- l-rahmnopyranosyl-β-d-glucopyranosyl)-3,3′,5,7-tetrahydroxy-4′-methoxyflavanone by means of spectral analyses using 1H-NMR, 13C-NMR, and 2D-NMR. Of these compounds, flavanone glycoside, hesperidin and narirutin were isolated as the main constituents. Thus, molasses is a promising source of flavonoid glycosides.
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References
Tatum JH, Berry RE (1972) Six new flavonoids from Citrus. Phytochemistry 11:2283–2288
Tatum JH, Berry RE (1978) Flavonoids of Citrus cultiver calamondin and synthetic 2′-β-dihydroxychalcones. Phytochemistry 17:447–449
Vandercook CE, Tisserat B (1989) Flavonoid changes in developing lemons grown in vivo and in vitro. Phytochemistry 28:799–803
Horie T, Tsukayama M, Yamada T, Miura I, Nakayama M (1986) Three flavone glycosides from Citrus sudachi. Phytochemistry 25:2621–2624
Champagne DE, Koul O, Isman MB, Scudder GGE, Towers GHN (1992) Biological activity of limonoids from the Rutales. Phytochemistry 31:923–925
Wu TS, Huang SC, Jong TT, Lai JS, Kuoh CS (1988) Coumarins, acridone alkaloids and a flavone from Citrus grandis. Phytochemistry 27:585–587
Sugiyama S, Umehara K, Kuroyanagi M, Ueno A, Taki T (1993) Studies on the differentiation inducers of myeloid leukemic cells from Citrus species. Chem Pharm Bull 41:714–719
Ju-ichi M (2005) Chemical study of Citrus plants in the search for cancer chemopreventive agents. Yakugaku Zasshi 125:231–254
Tanizawa H, Ohkawa Y, Takino Y, Miyase T, Ueno A, Kagheyama T, Hara S (1992) Studies on natural antioxidants in citrus species. I. Determination of antioxidative activities of citrus fruits. Chem Pharm Bull 40:1940–1942
Gorinstein S, Yamamoto K., Katrich E, Leontowicz H, Lojek A., Leontowicz M, Ciz M, Gshev I, Shalev U, Trakhtenberg S (2003) Antioxidative properties of Jaffa sweeties and grapefruit and their influence on lipid metabolism and plasma antioxidative potential in rats. Biosci Biotechnol Biochem 67:907–910
Champagne DE, Koul O, Isman MB, Scudder GGE, Towers GHN (1992) Biological activity of limonoids from the Rutaceae. Phytochemistry 31:377–394
Jayaprakasha GK, Singh RP, Pereira J, Sakariah KK (1997) Limonoids from Citrus reticulate and their moult inhibiting activity in mosquito Culex quinquefasciatus larvae. Phytochemistry 44:843–846
del Rio JA, Gomez P, Baidez AG, Acras MC, Botia JM, Ortuno A (2004) Changes in the levels of polymethoxyflavones and flavanones as part of the defense mechanism of Citrus sinensis (cv. Valencia Late) fruits against Phytophthora citrophthora. J Agric Food Chem 52:1913–1917
Sultana N, Armstrong JA, Waterman PG (1999) Benzpyran derivatives from the aerial parts of Eriostemon rhomboideus. Phytochemistry 52:895–900
Nakagawa H, Duan H, Takaishi Y (2001) Limonoids from Citrus sudachi. Chem Pharm Bull 49:649–651
Kinoshita K, Murase S (1971) Studies on the constituents of orange oil of Citrus natsudaidai Hayata. I. Structure of natsudaidain: 3-hydroxy-5,6,7,8,3′,4′-hexamethoxyflavone. Yakugaku Zasshi 91:1105–1108
Hasegawa S, Bennett RD, Herman Z, Fong CH, Ou P (1989) Limonoid glucosides in Citrus. Phytochemistry 28:1717–1720
Dreyer DL (1965) Citrus bitter principles—II. Tetrahedron 21:75–87
Matsubara Y, Yusa T, Sawabe A, Iizuka Y, Takekuma S, Yoshida Y (1991) Structures of new cyclic peptides in young unshiu (Citrus unshiu Marcov.), orange (Citrus sinensis Osbeck) and amanatsu (Citrus natsudaidai) peelings. Agric Biol Chem 55:2923–2929
Tatum JH, Berry RE (1987) Coniferin—an astringent glycoside in citrus. Phytochemistry 26:322–323
Hirai N, Yoshida R, Todoroki Y, Ohigashi H (2000) Biosynthesis of abscisic acid by the non-mevalonate pathway in plants, and by the mevalonate pathway in fungi. Biosci Biotechnol Biochem 64:1448–1458
Gaffield W (1970) Circular dichroism, optical rotatory dispersion and absolute configuration of flavanones, 3-hydroxyflavanones and their glucosides. Determination of aglycone chirality in flavanone glycosides. Tetrahedron 26:4093–4108
Liu H-W, Nakanishi K (1982) Pyranose benzoates. An additivity relation in the amplitudes of exciton-split CD curves. J Am Chem Soc 104:1178–1185
Nakanishi K, Kuroyanagi M, Nambu H, Oltz EM, Takeda R, Verdine GL, Zask A (1984) Recent applications of circular dichroism to structural problems, especially oligosaccharide structures. Pure Appl Chem 56:1031–1048
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Kuroyanagi, M., Ishii, H., Kawahara, N. et al. Flavonoid glycosides and limonoids from Citrus molasses. J Nat Med 62, 107–111 (2008). https://doi.org/10.1007/s11418-007-0198-8
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DOI: https://doi.org/10.1007/s11418-007-0198-8