Chemistry of Natural Compounds, Vol. 41, No. 6, 2005 MDIFIED CUMARINS. 19. SYNTHESIS F NEFLAVNE D-GLYCPYRANSIDES Ya. L. Garazd, 1 M. M. Garazd, 2 and V. P. Khilya 1 UDC 547.814.5 Neoflavone β-d-glucopyranosides, β-d-galactopyranosides, β-d-xylopyranosides, and α-darabinopyranosides were synthesized by Michael condensation of potassium salts of 7-hydroxy-4- arylcoumarins with acetobromosugars followed by deacetylation of the resulting peracetates. Key words: coumarins, neoflavones, 4-arylcoumarins, glycosides, glycosylation. More than 130 neoflavones with the 4-phenylcoumarin structure have been isolated from natural sources [1, 2]. Among the natural neoflavones are -glycosides with the carbohydrate at various positions of the coumarin. Examples of these are serratin 7-β-glucoside (1) isolated from Passiflora serratodigitata [3], 6--β-D-galactopyranosyldalbergin (2) isolated from Hesperethusa crenulata [4], and 5--(6 -acetyl-β-d-glucopyranosyl)-7,3,4 -trihydroxy-4-phenylcoumarin (3) produced by Hintonia latiflora [5]. The goal of our work was to synthesize -D-glycopyranosides of 7-hydroxy-4-arylcoumarins. 7-Hydroxy-4-arylcoumarins 4-7 that were needed for further transformations were prepared in high yields by Pechmann condensation of ethylbenzoylacetate and ethyl-4-methoxybenzoylacetate with polyphenols (resorcinol and 2-methylresorcinol) in the presence of conc. H 2 S 4 [6, 7]. The -glycopyranosides of the 7-hydroxy-4-arylcoumarins were synthesized using a method based on the reaction of a glycosyl donor and the potassium salts of the hydroxycoumarins in aqueous acetone with cooling (0 C) (modified Michael method [8, 9]) that was successfully used to synthesize a similar class of compounds [10]. The condensation of the potassium salts of 4-7 and acetobromosugars was carried out in concentrated aqueous acetone solution. Concentrated solutions of the phenolates of 4-7 were prepared using equivalent amounts of coumarins, KH solution (10%), and twice (relative to the volume of base solution) the amount of acetone. The glycosyl donors in these syntheses were the D-acetobromoglycopyranoses α-acetobromoglucose (Ac 4 GlupBr), α-acetobromogalactose (Ac 4 GalpBr), β-acetobromoarabinose (Ac 3 ArapBr), and α-acetobromoxylose (Ac 3 XylpBr). The syntheses produced in 36-52% yields the -peracetates of glucopyranosides 8-10, galactopyranosides 11-14, xylopyranoside 15, and arabinopyranoside 16, all of which have the sugar at the 7-position of the neoflavone. The structures of the prepared glycosides and the configurations of their anomeric centers were confirmed unambiguously by PMR spectroscopy. The PMR spectra of 8-16 contained signals for four (for glucosides and galactosides) or three (for arabinosides and xylosides) acetyl groups at 2.00-2.20 ppm and for the carbohydrates and aglycons. The PMR spectra of 8-10 exhibited a doublet at 5.12-5.18 ppm with SSCC J = 7.2-7.8 Hz for H-1 of the carbohydrate ring. A SSCC of this magnitude for H-1 and H-2 in carbohydrates is consistent with their trans-diaxial position in the ring [11]. Together with the chemical shift of H-1, this confirmed the β-configuration of the glucopyranosides. The CH 2-6 methylene protons of the glucosides were chemically nonequivalent and formed together with H-5 a group of signals near 4 ppm. The methylene protons resonated as two doublets of doublets at 4.17-4.19 and 4.30-4.31 ppm with SSCC J = 12.0-12.4 and J = 2.0-2.4 and J = 12.0-12.4 and 5.6-6.0, respectively. 1) Taras Shevchenko Kiev National University, 01033, Ukraine, Kiev, ul. Vladimirskaya, 64; 2) Institute of Bioorganic Chemistry and Petrochemistry, National Academy of Sciences of Ukraine, 02094, Ukraine, Kiev, ul. Murmanskaya, 1, e-mail: gmm@i.com.ua. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 546-550, November-December, 2005. riginal article submitted ctober 3, 2005. 0009-3130/05/4106-0663 2005 Springer Science+Business Media, Inc. 663
H Ac 4 GlupBr, KH H 2 -CH 3 CCH 3 Ac Ac Ac Ac MeNa MeH H H H H 4-7 R 8-10 R 17-19 R Ac 4 GalpBr, KH H 2 -CH 3 CCH 3 Ac Ac Ac MeNa MeH H H H Ac H 11-14 R 20-23 R 4, 8, 11, 17, 20: R = = H; 5, 9, 12, 18, 21: = Me, R = H; 6, 10, 13, 19, 22: = H, R = CH 3 7, 14, 23: = Me, R = CH 3 H 4 Ac 3 XylpBr, KH MeNa H 2 -CH 3 CCH Ac H 3 MeH Ac Ph H Ac H 15 24 Ac H Ac 3 ArapBr, KH MeNa H 2 -CH 3 CCH Ac MeH H 3 Ac H Ph 16 Ph 25 Ph PMR spectra of 11-14 contained a doublet for H-1 of the carbohydrate at 5.05-5.12 ppm with SSCC J = 7.8-8.1 Hz. This was consistent with the β-configuration of the prepared galactopyranosides. In contrast with the glucopyranosides, the CH 2-6 methylene protons of the galactopyranosides appeared as a complicated multiplet at 4.05-4.25 ppm. A doublet for H-1 in the PMR spectrum of triacetylxyloside 15 at 5.26 ppm with SSCC J = 7.2 Hz is consistent with the β-configuration of the anomeric center. The CH 2-5 methylene protons resonated as two doublet of doublets at 3.59 and 4.22 ppm with SSCC J = 12.0, J = 6.0 and J = 12.0, J = 2.1 Hz, respectively. The presence in the PMR spectrum of 16 of a doublet for H-1 at 5.20 ppm with SSCC J = 6.0 Hz confirmed that H-1 and H-2 were trans-diaxial. For a D-triacetylarabinoside, this occurs exclusively for the α-anomer, i.e., the arabinoside had the α-configuration. The CH 2-5 methylene protons resonated as two doublets of doublets at 3.83 and 4.15 ppm with SSCC J = 12.0, J = 2.1 and J = 12.0, J = 6.0 Hz, respectively. The IR spectra of 8-16 contained two bands at 1690-1760 cm -1 that were characteristic of acetyl C= and coumarin ring stretching vibrations, respectively. D-Glycopyranosides 17-25 with free hydroxyls were prepared in high yields by deacetylation of tetra- and tri-acetylglycopyranosides 8-16 using a modified Zemplen method (NaMe in absolute MeH). The PMR spectra of the synthesized glycosides contained signals for the carbohydrate and aglycon fragments and lacked signals for the acetyls in the starting peracetates. The presence in the PMR spectra of a doublet for anomeric H-1 with a typical SSCC confirmed that the 1,2-trans-diaxial orientation of H-1 and H-2 had been retained. The IR spectra of the glycopyranosides contained two bands at 3300-3400 and 1690-1720 cm -1 that were typical of hydroxyls and C= of the coumarin ring, respectively. 664
EXPERIMENTAL The course of reactions and the purity of products were monitored by TLC on Merck 60 F254 plates with elution by CHCl 3 :CH 3 H (9:1). Melting points were determined on a Kofler block. IR spectra were recorded on a Nicolet FTIR Nexus 475 spectrometer; PMR spectra, on Varian VXR-300 and Varian Mercury 400 spectrometers at 300 and 400 MHz, respectively, relative to TMS (internal standard). Elemental analyses agreed with those calculated. The syntheses of 7-hydroxy-4-arylcoumarins 4-7 have been published [6, 7]. Peracetylpyranosylbromides were prepared as before [12, 13]. 7-Peracetylglycopyranosyloxy-4-arylchromen-2-ones 8-16. A solution of 7-hydroxycoumarin (4-7, 10 mmol) in acetone (10 ml) and KH solution (5.6 ml, 10%) was stirred vigorously and cooled (0 C) for 30 min, treated in portions with stirring over 1 h with the appropriate peracetylpyranosylbromide (10 mmol), stirred for 4 h with cooling (0 C), left overnight at room temperature, diluted with CHCl 3 (50 ml), and worked up in a separatory funnel with KH solution (1 N, 2 50 ml) and water (50 ml). Acidification of the combined alkaline extracts regenerated unreacted hydroxycoumarin. The organic layer was dried over anhydrous MgS 4 and evaporated in a rotary evaporator. The oily product was crystallized from propan-2-ol. 7-(2,3,4,6-Tetra--acetyl-β-D-glucopyranosyloxy)-4-phenylchromen-2-one (8), yield 42%, C 29 H 28 12, mp 182-183.5 C. IR spectrum (KBr, cm -1 ): 1756, 1696, 1612, 1568, 1444, 1376, 1220, 1072. PMR spectrum (400 MHz, CDCl 3, δ, ppm, J/Hz): 2.05, 2.06, 2.07, 2.13 (12H, four s, four CH 3 C), 3.93 (1H, m, H-5 ), 4.19 (1H, dd, J = 12.4, J = 2.4, H-6 α), 4.31 (1H, dd, J = 12.4, J = 5.6, H-6 β), 5.17 (1H, d, J = 7.6, H-1 ), 5.19 (1H, m, H-4 ), 5.29-5.36 (2H, m, H-2, H-3 ), 6.28 (1H, s, H-3), 6.86 (1H, dd, J = 2.4, J = 8.8, H-6), 7.03 (1H, d, J = 2.4, H-8), 7.41 (1H, d, J = 8.8, H-5), 7.43 (2H, m, H-2, H-6 ), 7.53 (3H, m, H-3, H-4, H-5 ). 7-(2,3,4,6-Tetra--acetyl-β-D-glucopyranosyloxy)-8-methyl-4-phenylchromen-2-one (9), yield 46%, C 30 H 30 12, mp 168-169.5 C. IR spectrum (KBr, cm -1 ): 1756, 1692, 1606, 1452, 1374, 1248, 1040. PMR spectrum (300 MHz, CDCl 3, δ, ppm, J/Hz): 2.05, 2.06, 2.08 (12H, three s, four CH 3 C), 2.31 (3H, s, CH 3-8), 3.87 (1H, m, H-5 ), 4.17 (1H, dd, J = 12.0, J = 2.4, H-6 α), 4.30 (1H, dd, J = 12.0, J = 5.7, H-6 β), 5.12 (1H, d, J = 7.8, H-1 ), 5.19 (1H, t, J = 9.6, H-4 ), 5.30-5.40 (2H, m, H-2, H-3 ), 6.28 (1H, s, H-3), 6.91 (1H, dd, J = 8.7, H-6), 7.29 (1H, d, J = 8.7, H-5), 7.43 (2H, m, H-2, H-6 ), 7.50 (3H, m, H-3, H-4, H-5 ). 7-(2,3,4,6-Tetra--acetyl-β-D-glucopyranosyloxy)-4-(4-methoxyphenyl)chromen-2-one (10), yield 49%, C 30 H 30 13, mp 214.5-216 C. IR spectrum (KBr, cm -1 ): 1758, 1698, 1610, 1512, 1424, 1376, 1216, 1156, 1120, 1076. PMR spectrum (400 MHz, CDCl 3, δ, ppm, J/Hz): 2.05, 2.07, 2.13 (12H, three s, four CH 3 C), 3.89 (3H, s, CH 3-4 ), 3.93 (1H, m, H-5 ), 4.19 (1H, dd, J = 12.4, J = 2.0, H-6 α), 4.31 (1H, dd, J = 12.4, J = 6.0, H-6 β), 5.18 (1H, d, J = 7.2, H-1 ), 5.19 (1H, m, H-4 ), 5.29-5.36 (2H, m, H-2, H-3 ), 6.25 (1H, s, H-3), 6.86 (1H, dd, J = 2.4, J = 8.8, H-6), 7.01 (1H, d, J = 2.4, H-8), 7.04 (2H, d, J = 8.4, H-3, H-5 ), 7.39 (2H, d, J = 8.4, H-2, H-6 ), 7.48 (1H, d, J = 8.8, H-5). 7-(2,3,4,6-Tetra--acetyl-β-D-galactopyranosyloxy)-4-phenylchromen-2-one (11), yield 36%, C 29 H 28 12, light yellow oil. PMR spectrum (300 MHz, CDCl 3, δ, ppm, J/Hz): 2.06, 2.12, 2.18 (12H, three s, four CH 3 C), 4.00-4.28 (3H, m, H-5, CH 2-6 ), 5.05 (1H, d, J = 8.1, H-1 ), 5.15 (1H, dd, J = 3.3, J = 8.1, H-3 ), 5.45 (1H, d, J = 3.3, H-4 ), 5.57 (1H, dd, J = 8.1, J = 8.1, H-2 ), 6.28 (1H, s, H-3), 6.86 (1H, dd, J = 2.4, J = 8.7, H-6), 7.03 (1H, d, J = 2.4, H-8), 7.41 (1H, d, J = 8.7, H-5), 7.43 (2H, m, H-2, H-6 ), 7.53 (3H, m, H-3, H-4, H-5 ). 7-(2,3,4,6-Tetra--acetyl-β-D-galactopyranosyloxy)-8-methyl-4-phenylchromen-2-one (12), yield 46%, C 30 H 30 12, mp 187-188.5 C. IR spectrum (KBr, cm -1 ): 1758, 1696, 1604, 1444, 1370, 1222, 1070. PMR spectrum (300 MHz, CDCl 3, δ, ppm, J/Hz): 2.04, 2.09, 2.21 (12H, three s, four CH 3 C), 2.32 (3H, s, CH 3-8), 4.05-4.25 (3H, m, H-5, CH 2-6 ), 5.09 (1H, d, J = 8.1, H-1 ), 5.15 (1H, dd, J = 3.3, J = 8.1, H-3 ), 5.48 (1H, d, J = 3.3, H-4 ), 5.60 (1H, dd, J = 8.1, J = 8.1, H-2 ), 6.28 (1H, s, H-3), 6.92 (1H, d, J = 8.7, H-6), 7.29 (1H, d, J = 8.7, H-5), 7.43 (2H, m, H-2, H-6 ), 7.52 (3H, m, H-3, H-4, H-5 ). 665
7-(2,3,4,6-Tetra--acetyl-β-D-galactopyranosyloxy)-4-(4-methoxyphenyl)chromen-2-one (13), yield 39%, C 30 H 30 13, light yellow oil. PMR spectrum (300 MHz, CDCl 3, δ, ppm, J/Hz): 2.04, 2.10, 2.21 (12H, three s, four CH 3 C), 3.88 (3H, s, CH 3-4 ), 4.00-4.25 (3H, m, H-5, CH 2-6 ), 5.05 (1H, d, J = 8.1, H-1 ), 5.15 (1H, dd, J = 3.3, J = 8.1, H-3 ), 5.51 (1H, d, J = 3.6, H-4 ), 5.62 (1H, dd, J = 8.1, J = 8.1, H-2 ), 6.26 (1H, s, H-3), 6.86 (1H, dd, J = 2.4, J = 8.7, H-6), 7.01 (1H, d, J = 2.4, H-8), 7.04 (2H, d, J = 8.4, H-3, H-5 ), 7.39 (2H, d, J = 8.4, H-2, H-6 ), 7.48 (1H, d, J = 8.7, H-5). 7-(2,3,4,6-Tetra--acetyl-β-D-galactopyranosyloxy)-8-methyl-4-(4-methoxyphenyl)chromen-2-one (14), yield 52%, C 31 H 32 13, mp 128-129.5 C. IR spectrum (KBr, cm -1 ): 1758, 1698, 1604, 1514, 1370, 1248, 1080. PMR spectrum (400 MHz, CDCl 3, δ, ppm, J/Hz): 2.03, 2.05, 2.09, 2.21 (12H, four s, four CH 3 C), 2.32 (3H, s, CH 3-8), 3.89 (3H, s, CH 3-4 ), 4.05-4.25 (3H, m, H-5, CH 2-6 ), 5.08 (1H, d, J = 8.1, H-1 ), 5.13 (1H, dd, J = 3.3, J = 8.1, H-3 ), 5.48 (1H, d, J = 3.6, H-4 ), 5.60 (1H, dd, J = 8.1, J = 8.1, H-2 ), 6.25 (1H, s, H-3), 6.93 (1H, d, J = 8.7, H-6), 7.03 (2H, d, J = 8.7, H-3, H-5 ), 7.35 (1H, d, J = 8.7, H-5), 7.38 (2H, d, J = 8.7, H-2, H-6 ). 7-(2,3,4-Tri--acetyl-β-D-xylopyranosyloxy)-4-phenylchromen-2-one (15), yield 41%, C 26 H 24 10, mp 184-185 C. IR spectrum (KBr, cm -1 ): 1758, 1692, 1610, 1428, 1374, 1250, 1220, 1120, 1074. PMR spectrum (300 MHz, CDCl 3, δ, ppm, J/Hz): 2.11 (9H, s, CH 3 C-2, CH 3 C-3, CH 3 C-4 ), 3.59 (1H, dd, J = 12.0, J = 6.0, H-5 α), 4.22 (1H, dd, J = 12.0, J = 2.1, H-5 β), 5.04 (1H, m, H-4 ), 5.17-5.32 (2H, m, H-2, H-3 ), 5.26 (1H, d, J = 7.2, H-1 ), 6.27 (1H, s, H-3), 6.86 (1H, dd, J = 2.1, J = 8.7, H-6), 7.04 (1H, d, J = 2.1, H-8), 7.41 (1H, d, J = 8.7, H-5), 7.44 (2H, m, H-2, H-6 ), 7.52 (3H, m, H-3, H-4, H-5 ). 7-(2,3,4-Tri--acetyl-α-D-arabinopyranosyloxy)-4-pheylchromen-2-one (16), yield 44%, C 26 H 24 10, mp 185-186.5 C. IR spectrum (KBr, cm -1 ): 1744, 1696, 1612, 1374, 1248, 1236, 1218, 1090, 1048. PMR spectrum (300 MHz, CDCl 3, δ, ppm, J/Hz): 2.07, 2.09, 2.16 (9H, three s, four CH 3 C), 3.83 (1H, dd, J = 12.0, J = 2.1, H-5 α), 4.15 (1H, dd, J = 12.0, J = 6.0, H-5 β), 5.17 (1H, m, H-4 ), 5.20 (1H, d, J = 6.0, H-1 ), 5.36 (1H, m, H-3 ), 5.46 (1H, dd, J = 9.6, J = 10.2, H-2 ), 6.27 (1H, s, H-3), 6.89 (1H, dd, J = 2.4, J = 8.7, H-6), 7.06 (1H, d, J = 2.4, H-8), 7.41 (1H, d, J = 8.7, H-5), 7.44 (2H, m, H-2, H-6 ), 7.53 (3H, m, H-3, H-4, H-5 ). 7-Glycopyranosyloxy-4-arylchromen-2-ones 17-25. A solution of peracetate 8-16 (4 mmol) in absolute MeH (20 ml) was treated with NaMe (20 mg). The reaction mixture was boiled for 10-30 min (completion of reaction determined by TLC). The solid that precipitated on cooling (0 C) was filtered and washed with cold MeH. 7-(β-D-Glucopyranosyloxy)-4-phenylchromen-2-one (17), yield 87%, C 21 H 20 8, mp 199.5-201 C. IR spectrum (KBr, cm -1 ): 3436, 1704, 1686, 1620, 1552, 1384, 1292, 1166, 1076. PMR spectrum (300 MHz, DMS-d 6, δ, ppm, J/Hz): 3.18 (1H, m, H-4 ), 3.26 (2H, m, H-2, H-3 ), 3.44 (2H, m, H-5, H-6 α), 3.71 (1H, dd, J = 11.4, J = 2.4, H-6 β), 4.52 (1H, t, J = 5.7, H-6), 4.96 (1H, d, J = 7.5, H-1 ), 4.99 (1H, d, J = 4.2, H), 5.04 (1H, d, J = 3.9, H), 5.31 (1H, d, J = 4.2, H), 6.21 (1H, s, H-3), 6.97 (1H, dd, J = 2.4, J = 8.7, H-6), 7.12 (1H, d, J = 2.4, H-8), 7.37 (1H, d, J = 8.7, H-5), 7.50 (2H, m, H-2, H-6 ), 7.54 (3H, m, H-3, H-4, H-5 ). 7-(β-D-Glucopyranosyloxy)-8-methyl-4-phenylchromen-2-one (18), yield 94%, C 22 H 22 8, mp 219-220.5 C. IR spectrum (KBr, cm -1 ): 3456, 1708, 1690, 1604, 1562, 1448, 1380, 1274, 1074, 1042. PMR spectrum (300 MHz, DMS-d 6, δ, ppm, J/Hz): 2.33 (3H, s, CH 3-8), 3.15-3.38 (4H, m, H-2, H-3, H-4, H-5 ), 3.45 (1H, dd, J = 11.4, J = 4.8, H-6 α), 3.65 (1H, dd, J = 11.4, J = 2.4, H-6 β), 4.35 (1H, t, J = 5.7, H-6), 4.89 (1H, d, J = 7.2, H-1 ), 5.01 (1H, d, J = 4.2, H), 5.12 (1H, d, J = 4.2, H), 5.29 (1H, d, J = 4.2, H), 6.19 (1H, s, H-3), 7.08 (1H, dd, J = 9.0, H-6), 7.23 (1H, d, J = 9.0, H-5), 7.49 (2H, m, H-2, H-6 ), 7.54 (3H, m, H-3, H-4, H-5 ). 7-(β-D-Glucopyranosyloxy)-4-(4-methoxyphenyl)-chromen-2-one (19), yield 86%, C 22 H 22 9, mp 195-196.5 C. IR spectrum (KBr, cm -1 ): 3420, 2940, 1722, 1706, 1692, 1606, 1510, 1464, 1376, 1254, 1072. PMR spectrum (300 MHz, DMS-d 6, δ, ppm, J/Hz): 3.17 (1H, m, H-4 ), 3.27 (2H, m, H-2, H-3 ), 3.40 (1H, m, H-5 ), 3.44 (1H, dd, J = 11.4, J = 4.8, H-6 α), 3.72 (1H, dd, J = 11.4, J = 2.4, H-6 β), 3.85 (3H, s, CH 3-4 ), 4.47 (1H, t, J = 5.7, H-6), 4.96 (1H, d, J = 7.5, H-1 ), 4.98 (1H, d, J = 4.2, H), 5.05 (1H, d, J = 3.9, H), 5.31 (1H, d, J = 4.2, H), 6.16 (1H, s, H-3), 6.97 (1H, dd, J = 2.4, J = 8.7, H-6), 7.08 (2H, d, J = 8.7, H-3, H-5 ), 7.10 (1H, d, J = 2.4, H-8), 7.44 (2H, d, J = 8.7, H-2, H-6 ), 7.46 (1H, d, J = 8.7, H-5). 666
7-(β-D-Galactopyranosyloxy)-4-phenylchromen-2-one (20), yield 82%, C 21 H 20 8, mp 233-234.5 C. IR spectrum (KBr, cm -1 ): 3380, 1704, 1690, 1616, 1380, 1294, 1166, 1080. PMR spectrum (300 MHz, DMS-d 6, δ, ppm, J/Hz): 3.40-3.75 (6H, m, H-2, H-3, H-4, H-5, CH 2-6 ), 4.49 (1H, d, J = 4.5, H), 4.65 (1H, t, J = 5.7, H-6), 4.90 (1H, d, J = 4.5, H), 5.03 (1H, d, J = 7.5, H-1 ), 5.30 (1H, d, J = 4.2, H), 6.28 (1H, s, H-3), 7.00 (1H, dd, J = 2.1, J = 8.7, H-6), 7.16 (1H, d, J = 2.1, H-8), 7.37 (1H, d, J = 8.7, H-5), 7.50-7.60 (5H, m, H-2, H-3, H-4, H-5, H-6 ). 7-(β-D-Galactopyranosyloxy)-8-methyl-4-phenylchromen-2-one (21), yield 89%, C 22 H 22 8, mp 252-253.5 C. IR spectrum (KBr, cm -1 ): 3364, 1706, 1692, 1604, 1376, 1276, 1140, 1112, 1076. PMR spectrum (300 MHz, DMS-d 6, δ, ppm, J/Hz): 2.33 (3H, s, CH 3-8), 3.35-3.75 (6H, m, H-2, H-3, H-4, H-5, CH 2-6 ), 4.40 (1H, d, J = 4.5, H), 4.61 (1H, t, J = 5.7, H-6), 4.68 (1H, d, J = 4.5, H), 4.82 (1H, d, J = 7.5, H-1 ), 5.15 (1H, d, J = 4.2, H), 6.18 (1H, s, H-3), 7.08 (1H, dd, J = 9.0, H-6), 7.22 (1H, d, J = 9.0, H-5), 7.49 (2H, m, H-2, H-6 ), 7.54 (3H, m, H-3, H-4, H-5 ). 7-(β-D-Galactopyranosyloxy)-4-(4-methoxyphenyl)chromen-2-one (22), yield 91%, C 22 H 22 9, mp 235-236.5 C. IR spectrum (KBr, cm -1 ): 3396, 2912, 1706, 1690, 1608, 1548, 1510, 1380, 1250, 1212, 1088, 1032. PMR spectrum (300 MHz, DMS-d 6, δ, ppm, J/Hz): 3.38-3.74 (6H, m, H-2, H-3, H-4, H-5, CH 2-6 ), 3.85 (3H, s, CH 3-4 ), 4.45 (1H, d, J = 4.5, H), 4.58 (1H, t, J = 5.7, H-6), 4.79 (1H, d, J = 4.5, H), 4.93 (1H, d, J = 7.5, H-1 ), 5.16 (1H, d, J = 4.2, H), 6.15 (1H, s, H-3), 6.96 (1H, dd, J = 2.1, J = 8.7, H-6), 7.07 (2H, d, J = 8.7, H-3, H-5 ), 7.10 (1H, d, J = 2.1, H-8), 7.45 (3H, d, J = 8.7, H-5, H-2, H-6 ). 7-(β-D-Galactopyranosyloxy)-8-methyl-4-(4-methoxyphenyl)chromen-2-one (23), yield 93%, C 23 H 24 9, mp 245-246.5 C. IR spectrum (KBr, cm -1 ): 3420, 1704, 1690, 1608, 1510, 1372, 1284, 1254, 1072. PMR spectrum (300 MHz, DMS-d 6, δ, ppm, J/Hz): 2.33 (3H, s, CH 3-8), 3.38-3.75 (6H, m, H-2, H-3, H-4, H-5, CH 2-6 ), 3.85 (3H, s, CH 3-4 ), 4.45 (1H, d, J = 4.5, H), 4.53 (1H, t, J = 5.7, H-6), 4.75 (1H, d, J = 4.5, H), 4.83 (1H, d, J = 7.8, H-1 ), 5.18 (1H, d, J = 4.2, H), 6.14 (1H, s, H-3), 7.07 (3H, d, J = 8.7, H-6, H-3, H-5 ), 7.30 (1H, d, J = 8.7, H-5), 7.44 (2H, d, J = 8.7, H-2, H-6 ). 7-(β-D-Xylopyranosyloxy)-4-phenylchromen-2-one (24), yield 87%, C 20 H 18 7, mp 194-195.5 C. IR spectrum (KBr, cm -1 ): 3452, 1712, 1612, 1380, 1278, 1160, 1112, 1078. PMR spectrum (400 MHz, DMS-d 6, δ, ppm, J/Hz): 3.10-3.40 (4H, m, H-2, H-3, H-4, H-5 a), 3.76 (1H, m, H-5 e), 4.95 (1H, d, J = 6.9, H-1 ), 5.03 (1H, d, J = 4.5, H), 5.08 (1H, d, J = 3.9, H), 5.34 (1H, d, J = 4.8, H), 6.28 (1H, s, H-3), 7.00 (1H, dd, J = 2.1, J = 8.7, H-6), 7.16 (1H, d, J = 2.1, H-8), 7.37 (1H, d, J = 8.7, H-5), 7.50-7.60 (5H, m, H-2, H-3, H-4, H-5, H-6 ). 7-(α-D-Arabinopyranosyloxy)-4-phenylchromen-2-one (25), yield 82%, C 20 H 18 7, mp 126-127.5 C. IR spectrum (KBr, cm -1 ): 3408, 1712, 1610, 1376, 1208, 1152, 1074. PMR spectrum (400 MHz, DMS-d 6, δ, ppm, J/Hz): 3.48 (1H, m, H-4 ), 3.60-3.80 (4H, H-2, H-3, CH 2-5 ), 4.59 (1H, d, J = 4.2, H), 4.77 (1H, d, J = 5.4, H), 4.98 (1H, d, J = 6.9, H-1 ), 5.22 (1H, d, J = 4.8, H), 6.25 (1H, s, H-3), 7.01 (1H, dd, J = 2.1, J = 8.7, H-6), 7.15 (1H, d, J = 2.1, H-8), 7.38 (1H, d, J = 8.7, H-5), 7.50-7.60 (5H, m, H-2, H-3, H-4, H-5, H-6 ). ACKNWLEDGMENT We thank A "Eksimed" (Kiev, Ukraine) for assistance with the work. REFERENCES 1. R. D. H. Murray, The Naturally ccurring Coumarins, Springer, Vienna-New York (2002). 2. M. M. Garazd, Ya. L. Garazd, and V. P. Khilya, Khim. Prir. Soedin., 47 (2003). 3. A. Ulubelen, R. R. Kerr, and T. J. Mabry, Phytochemistry, 21, 1145 (1982). 4. D. Kumar and D. K. Mukharya, Acta Cienc. Indica, Chem., 16C(4), 411 (1990); Chem. Abstr., 116, 170107w (1992). 667
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