Licorice is one of the most important crude drugs in the world, and its major triterpene saponin, glycyrrhizin, is a well-known natural sweetener and pharmaceutical.2,3) Glycyrrhiza glabra and Glycyrrhiza uralensis are major glycyrrhizin-producing species and their distribution is different. [3][4][5] The former is distributed from southern Europe to the northwestern part of China, whereas the latter occurs from Central Asia to the northeastern part of China. Extensive chemical studies revealed that Glycyrrhiza plants produce not only glycyrrhizin but also many saponins and flavonoids, 3,6) and many species-specific flavonoids were also reported in the underground parts of respective Glycyrrhiza species.6-10) It is also noteworthy that flavonoid variations in leaves of Glycyrrhiza plants were observed. [10][11][12] In the present study, the characterization and variation of these index compounds from the leaves, which might be a good marker for revealing the differences among the three types of Glycyrrhiza plants, are discussed.
Results and DiscussionIsolation and Characterization of Flavonoids and Stilbenoids from Leaves of Glycyrrhiza uralensis and Intermediate-Type Plants Collected in Kazakhstan Air-dried leaves of G. uralensis collected in Kazakhstan were extracted with ethanol, and the ethyl acetate soluble fraction was subjected to a series of silica gel and reverse-phase silica gel (ODS) column chromatography to afford a new prenylated flavanone (1), and a new prenylated dihydrostilbene (6), together with four known compounds 2-5. The known compounds were identified as 8-dimethylallyleriodictyol (8-prenyleriodictyol) (2), 14) sophoraflavanone B (3), 15,16) gancaonin R (4), 17) and 6-dimethylallyleriodictyol (6-prenyleriodictyol) (5), 14) by comparison of their spectral data with published values.Compound 1, called licoleafol, was obtained as a colorless amorphous solid and showed a quasimolecular ion [MϩH] ϩ at m/z 373.1282 in high-resolution positive FAB-MS, which corresponds to the molecular formula C 20 H 21 O 7 . Compound 1 showed UV absorption at l max 291 nm and characteristic signals for a flavanone at d H 5.44 (dd, H-2), 3.08, and 2.81 (each dd, for H 2 -3) in its 1 H-NMR spectrum, and d C 79.4 (C-2) and 43.2 (C-3) in its 13 C-NMR spectrum. In addition, the 1 H-NMR spectrum showed signals due to a hydrogen-bonded hydroxyl group (OH-5) at d H 12.11 (s), one isolated aromatic proton at d H 6.02 (s), and three aromatic protons at d H 6.85 (2H, s) and 7.08 (1H, s). These signal patterns were similar to those of 8-dimethylallyleriodictyol (2) except for the splitting patterns of the latter three protons. However, comparative analysis of 13 C-NMR spectra of 1 and 2 revealed that both compounds have an identical flavanone structure including the substitution pattern of the B ring (Table 1). The difference between proton signal patterns of B rings in 1 and 2 was presumably due to the different anisotropic effect of the substituents in both compounds. The remaining substituent C 5 H 9 O was deduced to ...