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7.53 (1H s Himidazole), 7.06 (1H s Himidazole), 5.68 (1H s H12),
1.32 (3H s C27), 1.24 (3H s C25), 1.06 (3H s C23 or C24), 1.02
(6H d J = 7.81 C23 or C24 or C30), 0.93 (3H d J = 6.20 C29), 0.89
(3H s C26). 13C NMR (100 MHz CDCl3): d 216.91 (C3), 198.55
(C11), 173.82 (C28), 161.40 (C13), 136.89 (Cimidazole), 131.21
(C12), 130.14 (Cimidazole), 117.28 (Cimidazole), 60.68 (C9),
55.44 (C5), 54.06 (C18), 50.65 (C17), 47.69 (C4), 44.47 (C8), 43.86
(C14), 39.76 (C1), 38.78 (C20), 38.37 (C21), 36.73 (C10), 34.86,
34.14, 32.33 (C7), 30.11, 28.29 (C15), 26.34 (C23 or C24), 24.50,
21.36 (C23 or C24 or C30), 20.87 (C23 or C24 or C30), 20.80
(C27), 18.61, 18.36 (C26), 17.18 (C29), 15.57 (C25). EI-MS m/z:
519.00 (5) M+, 216.98 (29), 188.98 (100), 147.03 (62), 133.05
(22), 119.03 (33), 107.03 (23), 105.02 (32), 95.02 (43), 91.01 (37),
81.01 (30), 79.00 (25), 68.96 (55), 66.97 (33), 54.95 (26). Anal.
Calcd for C33H46N2O3.0.5EtOAc C, 74.70; H, 8.95; N, 4.98. Found:
C, 74.76; H, 9.35; N 4.84.
acetate from (45:55) to (20:80)], to afford 24 (46%). Mp 281.7–
285.0 °C. IR (film CHCl3): 3116.4, 2967.0, 2924.5, 2870.5, 1719.2,
1685.5, 1606.4, 1486.9, 1381.8, 1303.6, 1224.6 cmꢁ1 1H NMR
.
(400 MHz CDCl3): d 8.22 (1H s), 7.78 (1H s), 7.68 (1H s), 7.51 (1H
s), 7.21 (1H s), 7.14 (3H s), 7.02 (1H s), 5.27 (1H s), 2.86 (1H d
J = 15.90), 2.48 (1H d J = 11.04), 1.13 (6H s), 1.09 (3H s), 0.99 (3H
d J = 5.78), 0.95 (3H d J = 5.85), 0.86 (3H s), 0.71 (3H s). 13C NMR
(100 MHz CDCl3):
d 206.40, 174.59, 138.37, 137.15, 136.95,
130.76, 130.42, 129.61, 125.94, 122.67, 119.36, 117.37, 54.21,
52.42, 50.89, 45.09, 45.05, 43.06, 42.25, 39.26, 39.20, 38.57,
35.87, 35.42, 31.73, 30.32, 29.67, 27.61, 24.88, 23.51, 23.35,
22.33, 20.94, 20.03, 17.08, 16.36, 15.55. EI-MS m/z: 582.97 (7)
M+, 488.19 (35), 487.18 (100), 486.13 (27), 297.10 (31), 145.10
(30), 133.09 (39), 131.11 (32), 119.10 (46), 117.11 (32), 107.11
(41), 105.11 (56), 95.11 (33), 91.14 (64), 79.10 (48), 69.08 (73).
Anal. Calcd for C37H50N4O2.0.5EtOAc C, 74.72; H, 8.68; N, 8.94.
Found: C, 74.93; H, 9.08; N, 9.16.
4.1.21. 3,11-Dioxours-12-en-28-yl-20methyl-1H-imidazole-1-
carboxylate (22)
4.1.24. 28-(20-Methyl-1H-imidazol-1-yl)-3,28-dioxours-12-en-2-
(20-methyl-1H-imidazol-1-yl)-methylene (25)
Compound 22 was prepared using the same method as for 13
(300 mg 0.64 mmol), using 5 as a starting material and CBMI
(243.47 mg 1.28 mmol). The workup was performed after 6 h.
The solid was subjected to flash column chromatography [hex-
anes–ethyl acetate from (65:35) to (50:50)], to afford 22 (34%).
Mp 279.4–285.3 °C. IR (film CHCl3): 3182.9, 3120.3, 2927.4,
1871.5, 1704.8, 1659.5, 1549.5, 1511.9, 1460.8, 1384.6, 1365.4,
Compound 25 was prepared using the same method as for 13,
using 6 (300 mg 0.62 mmol) as a starting material and CBMI
(353.79 mg 1.86 mmol). The workup was performed after 24.5 h.
The solid was subjected to flash column chromatography [hex-
anes–ethyl acetate from (40:60) to (10:90)], to afford 25 (36%).
Mp 283.3–286.1 °C. IR (film CHCl3): 3116.4, 2952.5, 2870.5,
1270.9, 1248.7, 1232.3, 1215.9 cmꢁ1
.
1H NMR (400 MHz CDCl3): d
1717.3, 1684.5, 1603.5, 1540.9, 1411.6, 1383.7, 1247.7 cmꢁ1 1H
.
7.53 (1H s), 6.91 (1H s), 5.69 (1H s), 2.55 (3H s), 1.33 (3H s), 1.25
(3H s), 1.07 (3H s), 1.03 (3H s), 1.01 (3H d J = 6.18), 0.92 (6H s).
13C NMR (100 MHz CDCl3): d 216.94, 198.65, 175.42, 161.60,
149.73, 131.14, 127.69, 116.99, 60.65, 55.43, 54.24, 51.60, 47.71,
44.52, 43.98, 39.75, 38.98, 38.35, 36.72, 34.67, 34.15, 32.32,
30.11, 28.32, 26.33, 24.13, 21.38, 20.87, 20.76, 18.76, 18.61,
18.13, 17.28, 15.61. EI-MS m/z: 532.95 (7) M+, 423.01 (12),
216.89 (18), 190.96 (16), 189.96 (16), 188.96 (100), 173.09 (12),
147.10 (38), 119.09 (14), 105.10 (12), 95.15 (23), 91.12 (13),
83.14 (24), 81.10 (14). Anal. Calcd for C34H48N2O3 C, 76.65; H,
9.08; N, 5.26. Found: C, 76.26; H, 9.42; N, 4.86.
NMR (400 MHz CDCl3): d 7.67 (1H s C2CH), 7.53 (1H s H400or
H500), 7.16 (1H s H50), 7.00 (1H s H40), 6.87 (1H s H400 or H500),
5.28 (1H s H12), 2.86 (1H d J = 15.80 H1), 2.54 (4H s CH3 C200 and
H18), 2.47 (3H s CH3 C20), 1.15 (6H s C27 or C23 or C24), 1.12
(3H s C23 or C24), 1.00 (3H d J = 6.13 C30), 0.95 (3H d J = 6.13
C29), 0.87 (3H s C25), 0.77 (3H s C26). 13C NMR (100 MHz CDCl3):
d 206.50 (C3), 176.51 (C28), 149.35 (C200), 147.39 (C20), 137.37
(C13), 130.50 (C2CH), 128.68 (C40), 127.37, 125.87 (C12), 123.07
(C2), 118.11 (C50), 117.31, 54.16 (C18), 52.64 (C5), 51.84 (C17),
45.20 (C4), 45.15 (C9), 42.40 (C14), 42.36 (C1), 39.55 (C19), 39.39
(C8), 38.59 (C20), 36.03 (C10), 35.43 (C11), 31.78 (C7), 30.42
(C21), 29.66 (C3 or C24), 27.72 (C15), 24.75, 23.49, 23.28 (C27),
22.52 (C23 or C24), 21.07 (C30), 20.08 (C6), 17.93 (CH3 C200),
17.24 (C29), 16.90 (C26), 15.51 (C25), 13.75 (CH3 C20). EI-MS m/z:
611.12 (5) M+, 502.17 (38), 501.20 (100), 311.14 (14), 197.16
(25), 119.11 (10), 105.13 (11), 91.17 (12), 83.17 (14), 81.10 (9),
79.10 (8). Anal. Calcd for C39H54N4O2 C, 76.68; H, 8.91; N, 9.17.
Found C, 76.28; H, 9.31; N, 8.89.
4.1.22. 3,11-Dioxours-12-en-28-yl-4H-triazole-4-carboxylate
(23)
Compound 23 was prepared using the same method as for 14,
using 5 (300 mg 0.64 mmol) as a starting material and CDT
(315.13 mg 1.92 mmol). The workup was performed after 4 h.
The residue was subjected to flash column chromatography [hex-
anes–ethyl acetate from (80:20) to (70:30)], to afford 23 (43%).
Mp 169.3–172.7 °C. IR (film CHCl3): 3128.0, 2955.4, 2872.5,
1732.7, 1702.8, 1659.5, 1513.9, 1458.9, 1385.6, 1349.9,
4.1.25. 28-(4H-Triazol-4-yl)-3,28-dioxours-12-en-2-(4H-triazol-
4-yl)-methylene (26)
1275.7 cmꢁ1
.
1H NMR (400 MHz CDCl3): d 8.84 (1H s), 8.01 (1H
Compound 26 was prepared using the same method as for 14,
using 6 (300 mg 0.62 mmol) as a starting material and CDT
(407 mg 2.48 mmol). The workup was performed after 7.5 h. The
residue was subjected to flash column chromatography [hex-
anes–ethyl acetate from (80:20) to (70:30)], to afford 26 (21%).
Mp 245.5–251.1 °C. IR (film CHCl3): 3134.1, 2953.5, 2924.5,
2869.6, 1733.7, 1689.3, 1616.1, 1510.0, 1457.0, 1382.7, 1349.0,
s), 5.67 (1H s), 1.33 (3H s), 1.23 (3H s), 1.06 (3H s), 1.02 (3H s),
1.00 (3H d J = 6.34), 0.92 (3H d J = 6.38), 0.87 (3H s). 13C NMR
(100 MHz CDCl3):
d 216.98, 198.71, 174.14, 162.11, 152.65,
145.37, 130.97, 60.70, 55.41, 53.13, 51.00, 47.69, 44.46, 43.92,
39.73, 38.69, 38.30, 36.70, 34.15, 33.71, 32.31, 30.12, 28.67,
26.33, 22.94, 21.37, 20.89, 20.85, 18.62, 18.41, 17.10, 15.56. EI-
MS m/z: 519.84 (8) M+, 421.97 (46), 407.03 (43), 256.99 (100),
217.04 (73), 216.04 (71), 161.11 (45), 147.07 (32), 146.05 (42),
105.14 (31), 91.2 (39). Anal. Calcd for C32H45N3O3.0.5H2O C,
72.69; H, 8.77; N, 7.95. Found: C, 73.08; H, 8.85; N, 7.61.
1276.7, 1222.7, 1184.1 cmꢁ1 1H NMR (400 MHz CDCl3): d 8.82
.
(1H s), 8.37 (1H s), 8.10 (1H s), 7.99 (1H s), 7.80 (1H s), 5.31 (1H
s), 3.41 (1H d J = 17.27), 1.25 (2H), 1.16 (3H s), 1.15 (3H s), 1.11
(3H s), 0.99 (3H d J = 6.26), 0.96 (3H d J = 6.38), 0.88 (3H s), 0.72
(3H s). 13C NMR (100 MHz CDCl3): d 206.95, 174.81, 152.96,
152.24, 145.30, 137.60, 137.03, 128.37, 125.92, 125.29, 52.75,
51.39, 45.28 (2C), 44.99, 43.18, 42.40, 39.30, 39.21, 38.53, 35.74,
34.39, 31.87, 30.46, 29.66, 28.13, 23.59, 23.42 (2C), 22.48, 21.02,
20.16, 17.08, 16.43, 15.68. EI-MS m/z: 584.94 (4) M+, 488.01 (31),
487.00 (70), 202.01 (42), 190.07 (52), 189.09 (100), 187.13 (38),
133.03 (31), 132.03 (51), 119.05 (45), 117.08 (48). Anal. Calcd for
4.1.23. 28-(1H-Imidazol-1-yl)-3,28-dioxours-12-en-2-(1H-
imidazol-1-yl)-methylene (24)
Compound 24 was prepared using the same method as for 12,
using 6 (323 mg 0.67 mmol) as a starting material and CDI
(326 mg 2.06 mmol). The workup was performed after 5 h. The so-
lid was subjected to flash column chromatography [hexanes–ethyl