3.1 Characteristic data of compounds
3.1.1 Ethyl 3,3-dimethyl-13-hydroxytridecanoate (1)
Brown needle-shaped crystal (18 mg). Soluble in pet.ether. mp. 115 °C. Rf = 0.80 (100% pet.ether). 1H NMR (CDCl3 400 MHz): δ 4.05 (q, J = 7.17 Hz, 2H, H-14), 3.33 (dt, 2H, H-13), 1.98 (s, 2H, H-2), 1.54 (m, 2H, H-12), 1.2–1.34 (m, 16H, H-4,5,6,7,8,9,10,11), 0.81 (t, 3H, H-15), 0.79 (s, 3H, H-16, 17), and 1.62 (br s, 1H, 13-OH). ESI-MS (Negative ion): m/z 283.7 (M+ − 2H). Calculated for C17H34O3 = 286.2508.
3.1.2 Stigmasta-5,22-dien-3β-ol (2)
White needle-shaped crystal (22 mg). Soluble in CHCl3, mp 164 °C. Rf = 0.53 (pet.Ether: CH2Cl2 = 1:19). IR (KBr): 3676 (br,-OH str), 2960, 2852 (C-H str), 1558, 1601 (C-H bend), 1051, 960, 800 cm−1. 1H NMR (CDCl3 400 MHz): δ 5.35 (d, 1H, H-6), 5.15 (dd, 1H, J = 8.52 and 15.02 Hz, H-22), 5.03 (dd, 1H, J = 8.52 and 15.02 Hz, H-23), 3.51 (m,1H, H-3), 2.27 (m, 1H, H-20), 2.23 (m, 1H, H-24), 2.22 (m, 2H, H-4), 1.85 (m, 2×1H, H-25,7), 1.54 (m, 1H), 1.53 (m, 3×2H, H-15, 16, 17), 1.44 (m, 3×1H, 6×2H, H-2, 8, 9, 11, 12, 14), 1.25 (m, 2×2H, H-1, 28), 1.08 (d, 3H, H-21), 1.00 (s, 3H, H-19), 0.84 (d, 3H, J = 6.12 Hz, H-27), 0.82 (t, 3H, J = 6.98 Hz, H-29), 0.69 (s, 3H, H-18), 0.68 (d, 3H, J = 6.07 Hz, H-26). 13C NMR (CDCl3, 100 MHz): δ 140.79 (C-5), 138.32 (C-22), 129.33 (C-23), 121.72 (C-6), 71.83 (C-3), 56.91 (C-14), 56.02 (C-17), 51.27 (C-24), 50.21 (C-9), 42.35 (C-13), 42.26 (C-4), 40.48 (C-20), 39.73 (C-12), 37.30 (C-1), 36.55 (C-10), 31.94 (C-25,8), 31.71 (C-7,2), 28.93 (C-16), 25.42 (C-28), 24.39 (C-15), 21.23 (C-26,11), 21.10 (C-21), 19.41 (C-19), 19.01 (C-27), 12.25 (C-29), 12.07 (C-18). ESI-MS (positive ion): at m/z 413.6 (M+ +H). Calculated for C29H48O = 412.3705 [21].
3.1.3 tert.butyl tridecanoate (3)
White solid (6 mg). Soluble in CHCl3. mp 75 °C. Rf 0.77 in 100% DCM. IR (KBr):1707 (C=Ostrc), 2919 and 2843 (aliphatic C-H strc), 1464 and 1377 (aliphatic C-H bending), 1194 and 1096 (C-O strc) cm−1. 1H NMR (CDCl3 400 MHz): δ 2.34 (t, 2H, J = 7.40 Hz, H-2), 1.62 (m, 2H, H-3), 1.60 (m, 2H, H-4), 1.25 (s, 3×3H, H-15,16, 17), 1.24 (m, 8×2H, H-5, 6, 7, 8, 9, 10, 11, 12), 0.87 (t, 3H, J = 6.80 Hz, H-13). 13C NMR (CDCl3, 100 MHz): δ 178.30 (C-1), 76.72 (C-14), 33.78 (C-2), 31.96 (C-3), 29.73 (C-4, 5), 29.47 (C-6, 7), 29.39 (C-15, 16, 17), 29.27 (C-8,9), 29.10 (C-10), 24.74 (C-11), 22.72 (C-12), 14.13 (C-13). ESI-MS (positive ion): at m/z 271.3 (M+ +H). Calculated for C17H34O2 = 270.2559. On the basis of these spectral data, compound 3 was identified as tert.butyl tridecanoate (http://www.nmrdb.org) (Fig. 1).
3.1.4 6-α-hydroxy stigmast-20(21)-en-3-one (4)
Brown semi-solid (10 mg). Soluble in CHCl3. Rf = 0.52 (pet.ether: CHCl3 = 1:95). IR (KBr): 3450 (O-H str), 2940, 2869 (C-H str), 1686 (C=O str), 1641 (C=C str), 1034 (C-O str), 983, and 883 cm−1. 1H NMR (CDCl3 400 MHz): δ. 4.73 (br, s, 1H, H-21b), 4.60 (br, s, 1H, H-21a), 4.15 (distorted t, 1H, H-6), 3.65 (distorted t, 2H, H-2), 3.18 (br, 2H, H-4), 2.99 (distorted t, 2H, H-1), 2.71 (m, 1H, H-17), 2.27 (m, 1H, H-5), 2.18 (m, 1H, H-24), 1.95 (m,2H, H-11), 1.67 (m, 2H, H-22), 1.60 (m,1H, H-25), 1.52 (m, 2×2H, H-15,16), 1.37 (m, 2H, H-28), 1.24–1.36 (m, 2×2H, 2×1H, H-12, 7, 8, 9), 1.27 (m, 2H, H-23), 1.24 (m,1H, H-14), 0.96 (d, 3H, J = 7.0 Hz, H-26), 0.94 (d, 3H, J = 7.0 Hz, H-27), 0.87 (distorted t, 3H, H-29), 0.81 (s, 3H, H-18), 0.74 (s, 3H, H-19). 13C NMR (CDCl3, 100 MHz): δ 180.3 (C-3), 150.4 (C-20), 109.7 (C-21), 79.1 (C-6), 56.3 (C-13), 56.0 (C-17), 55.4 (C-9), 46.9 (C-4), 42.5 (C-14), 40.5 (C-22), 38.9 (C-10), 37.3 (C-5,8), 37.0 (C-1), 34.4 (C-2, 23), 32.2 (C-12), 31.9 (C-7), 29.4 (C-16), 27.4 (C-24), 24.9 (C-15, 28), 22.7 (C-11), 20.9 (C-27), 19.4 (C-26), 14.1 (C-29), 18.3 (C-18), 14.7 (C-19). On the basis of these spectral data, compound 4 was identified as 6-α-hydroxy stigmast-20(21)-en-3-one (Fig. 1).
3.1.5 18-(2′, 3′-dihydroxyphenyl)nonadec-17-en-2-ol (5)
White crystal (10 mg). Soluble in CHCl3, mp. 106–108 °C. Rf = 0.85 (pet.ether). IR (KBr): 3425 (O-H str), 2924 and 2852 (C-H aliphatic str.), 1558 and 1543 (C=C, aliphatic), 1506 (C=C, aromatic) cm−1. 1H NMR (CDCl3 400 MHz): δ 8.08 (d,1H, J = 8.0 Hz, H-4′), 7.60 (d, 1H, J = 7.2 Hz, H-6′), 7.47 (dd, 1H, J = 8.0 and 7.2 Hz, H- 5′), 5.42 (distorted triplet,1H, H-17), 3.9 (m, 1H, H-2), 2.35 (distorted triplet, 2H, H-16), 1.24–1.53 (m, 13×2H, H-3-15), 2.03 (s, 3H, H-19), 0.86 (d, 3H, J = 7.92 Hz, H-1). ESI-MS (positive ion) m/z 413.2 (M++Na) and GC-MS m/z 391 (M++H).
3.1.6 1-(N-propyl amino)-2-henecosanone (6)
White waxy solid (7 mg). Soluble in CHCl3. mp 67 °C. Rf 0.58 (in pet.ether: DCM = 9:1). IR (KBr): 2916 and 2848 (aliphatic C-H str.), 1701 (C=O str) cm−1. 1H NMR (CDCl3 400 MHz): δ 4.04 (s, br, 2H, H-1), 2.34 (t, 2H, J = 7.4 Hz, H-3, 1′), 1.63 (m, 2H, H-2′), 1.24 (m, 34H, H-4 to 20), 0.86 (t, 3H, J = 6.28 Hz, H-21, 3′), 2.16 (br, N-H). 13C NMR (CDCl3, 100 MHz): δ 204 (C-2), 67.5 (C-1), 57.6 (C-1′), 33.65 (C-3), 33.65, 31.95, 29.45, 29.37, 29.09, 24.43, 22.71 (C-4 to 20), 24.43 (C-2′),14.13 (C-21, 3′).
3.1.7 Stigmast–5(6), 20(21)-diene-3-one (7)
Brown semi-solid (3 mg). Soluble in CHCl3. Rf = 0.51 (pet.ether: CHCl3 = 1:4). 1H NMR (CDCl3 400 MHz): δ 5.35 (distorted triplet, 1H, H-6), 4.72 (br, s, 1H, H-21a), 4.59 (br, s, 1H, H-21b), 3.65 (s,2H, H-4), 3.17 (distorted triplet, 2H, H-2), 2.99 (distorted triplet,2H, H-1), 2.98 (m, 1H, H-17), 2.27 (m, 1H, H-24), 1.68 (m, 2H, H-7), 1.63 (m, 1H, H-25), 1.60 (distorted triplet, 2H, H-22), 1.51 (m, 2×2H, H-15, 16), 1.36 (m, 2×2H, H-23, 28), 1.24 (m, 3×1H, 2× 2H, H-8, 9, 11, 12, 14), 0.96 (d, 3H, J = 6.8 Hz, H-26), 0.94 (d, 3H, J = 6.8 Hz, H-27), 0.86 (t, 3H, J = 6.9 Hz, H-29), 0.81 (s, 3H, H-19), 0.74 (s, 3H, H-18).