yellow coloured amorphous powder, which on crystallization from hot acetone resulted in pale

Transcription

1 Supporting Information Hexane Extract. Compound I: Elution of column with hexane: dichloromethane (50:50 v/v; 200 ml), gave a pale yellow coloured amorphous powder, which on crystallization from hot acetone resulted in pale yellow needle shaped crystals. Rf = 0.81[TLC solvent system: toluene: acetic acid (170:30 v/v)], mp C. 1 H NMR: (CDCl 3 ) δ: (s, 1H, OH), (s, 1H, OH-8), (s, 1H, OH- 10), 5.96 (s, 1H, H-4), 2.68 (s, 3H, H-18), 2.65 (s, 3H, H-15), 2.09 (s, 3H, H-16), 1.75 (s, 3H, H- 13). 13 C NMR: (CDCl 3 )δ: (CO, C-14), (CO, C-17), (CO, C-1), (C q, C-3), (C q, C-5), (C q, C-8), (C q, C-10), (C q, C-6), (C q, C-9), (C q, C-2), (C q, C-11), (C q, C-7), 98.3 (CH-4), 59.1 (C q -12), 32.2 (CH 3-13), 31.3 (CH 3-18), 27.9 (CH 3-15), 7.6 (CH 3-16). (+)-ESI-MS: m/z 755 ([2 M + HCOO] +, 50), 389 ([M + HCOO] +, 100). (-)-ESI-MS: m/z 343 ([M - H] -, 60). (+)-HR-ESI-MS: m/z [M + Na] + (calcd for C 18 H 16 O 7 Na, ). Compound II: Further elution of column with hexane: dichloromethane (1:1,100 ml) gave a colourless crystalline compound, which was further purified by crystallization from toluene. Rf = 0.75[TLC solvent system: toluene: acetic acid (170:30 v/v)]. mp o C. 1 H NMR (CDCl 3 ) δ :12.53 (s, 1H, 4-OH), (s, 1H, 2-OH), (s, 1H, 2 -OH), (s,1h,h-8), 6.49 (s, 1H, H-5 ), 6.38 (s, 1H, H-5), 3.96 (s, 3H, H-10 ), 2.67 (s, 3H, H-9), 2.52 (s, 3H, H-9 ), 2.07 (s, 3H, H-8 ). 13 C NMR (CDCl 3 ) δ: (CO, C-8), (CO, C-7 ), (CO, C-7), (C q, C-2), (C q, C-4), (C q, C-2 ), (C q, C-6), (C q, C-4 ), (C q, C-6 ), (C q, C-3 ), (CH, C-5 ), (CH, C-5), (C q -1 ), (C q -3), (C q -1), 52.3 (CH 3-10 ), 25.6 (CH 3-9), 24.1 (CH 3-9 ), 9.4 (CH 3-8 ). (+)-HR-ESIMS: m/z [M + Na] + (calculated for C 19 H 18 O 8 Na).

2 Compound III: Elution of column with dichloromethane (100mL) gave colourless needles, which was further purified by recrystallization from hexane. Rf = 0.32 [TLC solvent system: toluene: acetic acid (170:30 v/v)]. mp o C. Optical rotation [α] D : 2.37 (c 3.0, MeOH). 1 H- NMR : (CDCl 3 ) δ: 11.0 (s, 1H), 6.43 (d, 1H, J= 2.85 Hz), 6.03 (d, 1H, J= 2.85Hz), 4.81 (q, 1H, J=5.5; 5.6 Hz), 1.68 (m, 2H, 1H, J= 5.4; 2.7 Hz), (m, 22H), 0.89 ( t, 3H, J= 5.9 Hz). 13 C- NMR: (CDCl 3 ) δ: (CO, C-1), (CO, C-4), (C-3), (CH 2, C-1 ), 78.8 (CH, C-5), 49.4 (CH, C-2), 35.7 (CH 2, C-12 ), 31.9 (CH 2, C-11 ), 29.7, 29.6, 29.6, 29.5, 29.4, 29.4, 29.0, 29.2, 24.7, 22.7 (CH 2, C-2 -C-10 ) and 14.2(CH 3, C-14 ). (+)-ESIMS: m/z 325 ([M + H] +, HR-ESIMS: m/z [M-H] + calculated for C 19 H 31 O 4 calculated for C 19 H 33 O 4 [M + H] +. Ethyl acetate Extract. Compound IV: The ethyl acetate extract was subjected to column chromatography. Elution of column with hexane: dichloromethane (75:25, v/v, 200 ml) gave a colourless crystalline compound with a characteristic smell (smell of oak moss), which was further purified by crystallization from hot hexane. Rf=0.54 [TLC solvent system: toluene: acetic acid (170:30 v/v)] mp o C. 1 H NMR: (CD 3 OD) δ: 6.17 (s,1h, H-5), 3.84 (s, 3H, OCH 3 ), 2.36 (s, 3H, H-8), 1.98 (s, 3H, H-7). 13 C NMR: (CD 3 OD) δ: (CO, C-1 ), (C q, C-2), (C q, C-4), (C q, C-6), (CH, C-5), (C q, C-3), (C q, C-1), 51.9 (OCH 3 ), 24.3 (CH 3-8), 8.0 (CH 3-7). (+)-EIMS: m/z 196 ([M] + 26), 164 (88), 136 (100), 107 (16). Compound V: Further elution of column with hexane : dichloromethane (50:50, v/v; 200mL) gave another colorless crystalline compound, purified by crystallization from hexane. Rf= 0.65 [TLC solvent system: toluene: acetic acid (170:30 v/v)]. 1 H NMR: (CDCl 3 ) δ: (s, 1H, 4- OH), (s, 1H, 2-OH), (s, 1H, CHO), 6.26 (s, 1H, CH-5), 4.40 (quartet, 2H, CH 3-3ʹ), 2.52 (s, 3H, CH 3, C-5ʹ), 1.42 (t, 3H, CH 3-4ʹ). 13 C NMR : (CDCl 3 ) δ: 193.7(CO, C-1ʹ), 171.4

3 (CO, C-2ʹ, ( C q, C-4), (C q, C-2ʹ), (C q, C-6), (CH, C-5), (C q, C-1), (C q, C-3), 61.9 (O-ʹCH 2, C-3ʹ ), 25.4 (C-5ʹ), 14.3 (CH 3, C-4ʹ). (+)-ESI MS: m/z 224 [M] +, 195 (24), 177 (26), 149 (100), 121 (10). (+)-HR-ESIMS: m/z , [M+Na] + calculated for C 11 H 12 O 5 Na. Compound VI: A colourless crystalline compound was isolated by elution of column with dichloromethane (200 ml). Rf= 0.41 [TLC solvent system: toluene: acetic acid (170:30 v/v)]. mp o C. 1 H NMR: (CDCl 3 ) δ: (s, 1H, 2-OH), 6.24 (s, 1H, H-5), 6.20 (S, 1H, H-3), 5.05 (s, 1H, 4-OH), 4.38 (quart, 2H, H-8), 2.44 (s, 3H, H-6), 1.39 (t, 3H, H-9). 13 C NMR: (CDCl 3 ) δ:171.5 (CO, C-7), (C q, C-2), (C q, C-4), (C q, C-6), (CH, C-5), (CH, C-3), (C q, C-1), 51.8 ( CH 2, C-8), 24.1 (CH 3, C-9), 14.3 (CH 3, C-10). (+)EI MS: m/z 196, 150 (100), 164 (15), 136 (10), 122 (25). Compound VII: A colourless crystalline compound was obtained when column was eluted with hexane: dichloromethane (1:1, 200 ml). Rf = 0.60 [TLC solvent system: toluene: acetic acid (170:30 v/v)]. mp C. 1 H NMR: (CD 3 OD) δ: (s, 1H, 2-OH), (s, 1H, 4-OH), 10.31(s, 1H, C-3ʹ) 6.26 (s, 1H, CH-5), 3.93 (s, 3H, O-CH 3 ), 2.50 (s, 3H, CH 3-6). 13 C NMR : (CD 3 OD) δ: (CO, C-3ʹ), (CO, C-1ʹ), (Cq, C-4), (Cq, C-2), (Cq, C-6), (Cq,C-5), (Cq, C-3), (Cq, C-1), 52.3 (O-CH 3, C-2ʹ ), 25.3 (CH 3, C-6). (- )-ESI MS: m/z [M-H] -, [2M-2H+Na] -, (-)-HR-ESI MS m/z [M-H] - calculated for C 10 H 10 O 5. Compound VIII: Elution of column with dichloromethane (200mL) gave orange coloured compound, purified by crystallization from ethyl acetate. Rf = 0.55 [TLC solvent system: toluene: acetic acid (170:30 v/v)] mp o C. 1 H NMR: (CDCl 3 ) δ: (1H, OH), 6.86 (2H, d), 3.90 (s, 3H, O-CH 3 ), 3.91 (s, 3H, O-CH 3 ), 2.95 (s, 3H, CH 3 ). 13 C NMR: (CDCl 3 )

4 δ:182.4 (CO, C-9), (Cq, C-3), (Cq, C-13), (Cq, C-6), (C-OH, C-1), (Cq, C-11), (Cq, C-8),115.4 (CH, C-7), (C-10), 104.1(C-12), 98.4 (CH-5), 96.7 (CH-4), 98.7 (CH-2), 55.7 (O-CH 3 ), 55.6 (O-CH 3 ), 23.5 (C-8, CH 3 ). EIMS: m/z 196 (M + ). Compound IX. Column on elution with dichloromethane:acetone (95:5 v/v, 200mL) gave a colourless solid, purified by recrystallization from methanol as needle shaped crystals. Rf=0.72 [TLC solvent system: toluene: acetic acid (170:30 v/v)]. 1 H NMR: (CDCl 3 ) δ: (1H, C- OH), 6.50 (1H, CH-5), 5.40 (1H, C-1ʹ (OH)), 3.90 (s, 3H, O-CH 3 ), 2.70 (s, 3H, CH 3 ), 2.30 (s, 3H, CH 3 ). 13 C NMR: (CDCl 3 ) δ: (CO, C-1ʹ), (C-2, C-OH), (Cq, C-4), (Cq, C-6), (C-3), (Cq, C-1), (CH-5), 51.9 (O-CH 3, C-4ʹ), 24.1 (C-2ʹ, CH 3 ), 7.7 (C-3ʹ, CH 3 ). EIMS: m/z: 286(M + ) Compound X. Further elution of column with dichloromethane : acetone (90:10 v/v, 200mL) gave a white amorphous solid, recrystallized from aqueous acetone as colourless plates. Rf=0.87 [TLC solvent system: toluene: acetic acid (170:30 v/v)]. mp o C(dec.). 1 H NMR : (DMSO-d 6 ) δ: (s, 1H, 2-OH, 2ʹ-OH), (s,1h, 7ʹ-OH), (s, 1H, H-8), 6.45 (s,1h, H-5ʹ), 6.38 (s, 1H, H-5), 3.88 (s,3h, H-9), 2.35 (s,3h, H-9ʹ), 2.04 (s, 3H, H-8ʹ), 1.94 (s,3h, H-10). 13 C NMR: (DMSO-d 6 ) δ (CO, C-8), (CO, C-7ʹ), (CO, C-7), (Cq, C-4), (Cq, C-2ʹ), 161.7(Cq, C-2), (Cq, C-4ʹ), (Cq, C-6), (Cq, C-6ʹ), (CH, C-5ʹ), (Cq, C-1ʹ), (CH, C-5), (Cq,C-1), 52.2 (CH 3, C-9), 23.3 (CH 3-9ʹ), 21.1 (CH 3-10), 9.2 (CH 3-8ʹ). (+)-ESIMS: [ M+Na] +, [2M+Na] +, (+)- HR-ESIMS: m/z [M + Na] + calculated for [C 19 H 18 O 8 Na]. Compound XI. Ethyl acetate extract on evaporation gave a brown coloured amorphous solid, which was found to be insoluble in most of the organic solvents. Therefore, it was purified by

5 crystallization from acetone: water (80:20). Rf=0.13 [TLC solvent system: toluene: acetic acid (170:30 v/v)]. mp o C. 1 H NMR: (DMSO-d 6 ) δ: (1H, s, C-2ʹ, OH), (2H, s, C-3 and C-6ʹ, CHO), 8.30 (1H, s, C-4, OH), 6.86 (1H, s, C-3ʹ, OH), 6.80 (1H, s, H-5), 4.64 (2H, s, 13 CH ), 2.44 (3H, s, C-6, CH ). 13 C NMR: (DMSO-d 6 ) δ: (C-3, CHO), (C- 2), (C-4), (C-7, CO ), (C-7, CO ), (C-6 or C-2ʹ), (C-6 or C- 2 ), (C-4 ), (C-5 or C-6 ), (C-5 or C-6 ), (C-3 ), (C-5), (C- 1), (C-3), (C-1 ), 94.9 (C-6, CHO), 52.7 (C-3, CH OH), 21.4 (C-6, CH ) (XI, Figure 1). (-)-ESIMS: m/z [M-H] - :(-)-HR-ESIMS: m/z: [C 18 H 12 O 10 ].