#### 3.4. Spectral Data

Stigmasterol (**1**). White needles, m.p. 169–170 °C, EIMS: m/z 412 [M]^{+}. ^{1}H-NMR (CDCl_{3}, 500 MHz): δ_{H} 3.55 (m, H-3), 5.38 (brs, H-6), 0.69 (s, H-18),1.02 (s, H-19), 0.93 (d, J = 6.1 Hz, H-21), 5.18 (dd, J = 15.4, 8.0 Hz, H-22), 5.11 (dd, J = 15.4, 8.0 Hz, H-23), 0.84 (d, J = 7.3 Hz, H-26), 0.84 (d, J = 7.3 Hz, H-27), 0.86 (t, J = 7.1 Hz, H-29). ^{13}C-NMR (CDCl_{3}, 125 MHz): δ_{C} 37.2 (C-1), 31.8 (C-2), 71.9 (C-3), 39.4 (C-4), 140.8 (C-5), 121.8 (C-6), 29.1 (C-7), 31.9 (C-8), 50.1 (C-9), 35.9 (C-10), 20.6 (C-11), 41.0 (C-12), 42.2 (C-13), 56.1 (C-14), 23.3 (C-15), 24.6 (C-16), 56.8 (C-17), 11.9 (C-18), 18.9 (C-19), 39.8 (C-20), 20.9 (C-21), 138.4 (C-22), 129.3 (C-23), 51.2 (C-24), 31.9 (C-25), 19.4 (C-26), 19.8 (C-27), 26.7 (C-28), 12.0 (C-29).

α-Irone (**2**). Colorless oil. EIMS: m/z 206 [M]^{+}. ^{1}H-NMR (CDCl_{3}, 500 MHz): δ_{H} 2.33 (s, H-1), 6.10 (d, J = 15.8 Hz, H-3), 6.66 (dd, J = 15.8, 11.0 Hz, H-4), 2.59 (m, H-5), 5.54 (brs, H-7), 1.98, 1.78 (2H each m, H-8), 1.52 (m, H-9), 0.88 (s, H-11), 1.63 (s, H-12), 0.73 (s, H-13), 0.88 (d, J = 6.5 Hz, H-14). ^{13}C-NMR (CDCl_{3}, 125 MHz): δ_{C} 27.0 (C-1), 198.3 (C-2), 133.6 (C-3), 149.6 (C-4), 56.0 (C-5), 132.0 (C-6), 123.1 (C-7), 31.8 (C-8), 37.9 (C-9), 35.8 (C-10), 15.4 (C-11), 23.0 (C-12), 15.0 (C-13), 26.6 (C-14).

γ-Irone (**3**). Colorless oil. EIMS: m/z 206 [M]^{+}. ^{1}H-NMR (CDCl_{3}, 500 MHz): δ_{H} 2.37 (s, H-1), 6.15 (d, J = 16.0 Hz, H-3), 6.95 (dd, J = 16.0, 10.5 Hz, H-4), 2.85 (m, H-5), 2.36, 2.15 (2H each m, H-7), 1.56, 1.25 (2H each m, H-8), 1.45 (m, H-9), 0.88 (s, H-11), 4.82, 4.45 (2 H each brs, H-12), 0.74 (s, H-13), 0.88 (d, J = 6.5 Hz, H-14). ^{13}C-NMR (CDCl_{3}, 125 MHz): δ_{C} 27.3 (C-1), 198.3 (C-2), 134.3 (C-3), 147.3 (C-4), 57.8 (C-5), 148.8 (C-6), 36.3 (C-7), 31.9 (C-8), 41.9 (C-9), 38.8 (C-10), 15.9 (C-11), 108.7 (C-12), 14.1 (C-13), 27.7 (C-14).

3-Hydroxy-5-methoxyacetophenone (**4**). Colorless crystals, (MeOH), R_{f} = 0.78 (solvent system I), m.p. 188–189 °C. EIMS: m/z 166 [M]^{+}. ^{1}H-NMR (CDCl_{3}, 500 MHz): δ_{H} 7.55 (d, J = 1.5 Hz, H-2), 6.97 (d, J = 1.5 Hz, H-4), 7.55 (d, J = 1.5 Hz, H-6), 2.58 (s, H-8), 6.22 (s, 3-OH), 3.97 (s, 5-OCH_{3}). ^{13}C-NMR (CDCl_{3}, 125 MHz): δ_{C} 130.2 (C-1), 124.1 (C-2), 150.4 (C-3), 113.8 (C-4), 146.6 (C-5), 109.7 (C-6), 196.9 (C-7), 26.2 (C-8), 56.1 (5-OCH_{3}).

Irilone (**5**). Yellow needles (MeOH), m.p. 233–234 °C. EIMS: 298 [M]^{+}. λ_{max} 205, 261, and 324 nm. ^{1}H-NMR (DMSO-d_{6}, 500 MHz): δ_{H} 8.44 (s, H-2), 6.90 (s, H-8), 7.40 (2 H, d, J = 8.0 Hz, H-2', 6'), 6.83 (2 H, d, J = 8.0 Hz, H-3', 5'), 6.19 (s, -O-CH_{2}-O-), 9.65 (s, 4'-OH), 12.94 (s, 5-OH). ^{13}C-NMR (DMSO-d_{6}, 125 MHz): δ_{C} 154.7 (C-2), 122.1 (C-3), 180.9 (C-4), 141.3 (C-5), 129.5 (C-6), 153.9 (C-7), 89.5 (C-8), 152.9 (C-9), 107.4 (C-10), 120.9 (C-1'), 130.2 (C-2', 6'), 115.1 (C-3', 5'), 157.5 (C-4'), 102.8 (-O-CH_{2}-O-).

Irisolidone (**6**). Yellow amorphous powder. EIMS: m/z 314 [M]^{+}. UV (MeOH) λ_{max} nm: 207, 264, and 328. ^{1}H-NMR (DMSO-d_{6}, 500 MHz): δ_{H} 7.88 (s, H-2), 6.59 (s, H-8), 7.47 (d, J = 8.5 Hz, H-2', 6'), 6.99 (d, J = 8.5 Hz, H-3', 5'), 3.86 (s, 4'-OCH_{3}), 4.05 (s, 6-OCH_{3}), 13.15 (s, 5-OH). ^{13}C-NMR (DMSO-d_{6}, 125 MHz): δ_{C} 153.5 (C-2), 123.1 (C-3), 181.4 (C-4), 152.8 (C-5), 130.4 (C-6), 152.7 (C-7), 93.2 (C-8), 155.3 (C-9), 106.4 (C-10), 122.9 (C-1'), 130.2 (C-2', 6'), 159.7 (C-4'), 114.1 (C-3', 5'), 55.4 (4'-OCH_{3}), 60.9 (6-OCH_{3}).

Irigenin S (

**7**). Yellow needles (MeOH), R

_{f} = 0.47 (solvent system II), m.p. 192–193 °C. UV (MeOH) λ

_{max} nm: 201, 265, and 323. IR ν

_{max} (cm

^{−1}): 3437, 2956, 1651, and 1065. HRESIMS:

m/z 375.1002 (calcd for C

_{19}H

_{19}O

_{8} 375.1001). NMR spectral data, see

Table 1.

Irigenin (**8**). Yellow needles (MeOH), m.p. 185–186 °C. UV (MeOH) λ_{max} nm: 203, 263, and 323 nm. EIMS: m/z 360 [M]^{+}. ^{1}H-NMR (DMSO-d_{6}, 500 MHz): δ_{H} 8.40 (s, H-2), 6.52 (s, H-8), 6.72 (d, J = 1.5 Hz, H-2'), 6.71 (d, J = 1.5 Hz, H-6'), 3.70 (s, 4'-OCH_{3}), 3.79 (s, 5'-OCH_{3}), 3.76 (s, 6-OCH_{3}), 9.31 (s, 3'-OH), 13.01 (s, 5-OH), 10.90 (s, 7-OH). ^{13}C-NMR (DMSO-d_{6}, 125 MHz): δ_{C} 154.8 (C-2), 126.0 (C-3), 180.3 (C-4), 153.3 (C-5), 131.4 (C-6), 157.5 (C-7), 93.9 (C-8), 152.8 (C-9), 104.8 (C-10), 121.7 (C-1'), 110.3 (C-2'), 150.2 (C-3'), 136.3 (C-4'), 152.6 (C-5'), 104.4 (C-6'), 59.9 (4'-OCH_{3}), 55.7 (5'-OCH_{3}), 59.9 (6-OCH_{3}).

Stigmasterol-3-O-β-glucoside (**9**). White amorphous powder. FABMS: m/z 575 [M+H]^{+}. ^{1}H-NMR (C_{5}D_{5}N, 500 MHz): δ_{H} 3.97 (m, H-3), 0.62 (s, H-18), 1.21 (s, H-19), 0.96–0.81 (methyl groups), 5.06 (d, J = 7.6 Hz, H-1'), 4.58–3.86 (m, sugar protons). ^{13}C-NMR (C_{5}D_{5}N, 125 MHz): δ_{C} 38.0 (C-1), 31.1 (C-2), 78.9 (C-3), 40.4 (C-4), 141.4 (C-5), 122.4 (C-6), 32.7 (C-7), 32.5 (C-8), 50.8 (C-9), 37.4 (C-10), 21.8 (C-11), 39.5 (C-12), 43.0 (C-13), 57.3 (C-14), 25.0 (C-15), 23.7 (C-16), 56.7 (C-17), 11.6 (C-18), 19.9 (C-19), 39.8 (C-20), 19.5 (C-21), 133.6 (C-22), 129.8 (C-23), 46.5 (C-24), 29.9 (C-25), 19.7 (C-26), 20.5 (C-27), 24.5 (C-28), 12.5 (C-29), 103.0 (C-1'), 72.2 (C-2'), 75.8 (C-3'), 68.7 (C-4'), 78.7 (C-5'), 63.3 (C-6').

Irilone 4'-O-β-D-glucopyranoside (**10**). Yellow amorphous powder. UV (MeOH) λ_{max} nm: 203, 271, and 337 nm. FABMS: m/z 461 [M+H]^{+}, 299 [M-162 (hexose unit)+H]^{+}. ^{1}H-NMR (DMSO-d_{6}, 500 MHz): δ_{H} 8.51 (s, H-2), 7.01 (s, H-8), 7.34 (2 H, d, J = 8.5 Hz, H-2', 6'), 6.81 (2 H, d, J = 8.5 Hz, H-3', 5'), 6.19 (s, -O-CH_{2}-O-), 13.42 (s, 5-OH), 4.98 (d, J = 6.7 Hz, H-1”). ^{13}C-NMR (DMSO-d_{6}, 125 MHz): δ_{C} 155.4 (C-2), 123.0 (C-3), 181.0 (C-4), 139.8 (C-5), 129.4 (C-6), 153.5 (C-7), 93.6 (C-8), 151.7 (C-9), 106.9 (C-10), 120.9 (C-1'), 130.2 (C-2', 6'), 114.8 (C-3', 5'), 157.9 (C-4'), 102.6 (-O-CH_{2}-O-), 100.9 (C-1”), 73.6 (C-2”), 77.4 (C-3”), 69.8 (C-4”), 76.7 (C-5”), 60.6 (C-6”).

Iridin (**11**). Yellow needles, m.p. 210–211 °C. UV (MeOH) λ_{max} nm: 203, 263, and 335 nm. FABMS: m/z 523 [M+H]^{+}, 361 [M-162 (hexose unit)+H]^{+}. ^{1}H-NMR (DMSO-d_{6}, 500 MHz): δ_{H} 8.51 (s, H-2), 6.70 (s, H-8), 6.91 (brs, H-2'), 6.74 (brs, H-6'), 3.71 s (s, 4'-OCH_{3}), 3.80 (s, 5'-OCH_{3}), 3.78 (s, 6-OCH_{3}), 9.30 (s, 3'-OH), 12.95 (s, 5-OH), 5.11 (d, J = 6.7 Hz, H-1”). ^{13}C-NMR (DMSO-d_{6}, 125 MHz): δ_{C} 155.4 (C-2), 125.9 (C-3), 180.5 (C-4), 152.9 (C-5), 132.5 (C-6), 156.6 (C-7), 94.0 (C-8), 152.4 (C-9), 104.5 (C-10), 122.0 (C-1'), 110.3 (C-2'), 150.3 (C-3'), 136.4 (C-4'), 152.9 (C-5'), 104.5 (C-6'), 100.1 (C-1'), 73.1 (C-2'), 77.3 (C-3”), 69.6 (C-4”), 76.7 (C-5”), 60.3 (C-6”).

Iriside A (

**12**). Yellow oil, R

_{f} = 0.42 (solvent system III), [α]

_{D} +72.6° (

c 0.3, MeOH). IR ν

_{max} (cm

^{−1}): 3452, 2945, 1455, 1103, 983. HRFABMS:

m/

z 179.0840 (

calc. for C

_{7}H

_{15}O

_{5}, 179.0841). NMR spectral data, see

Table 1.