13
C NMR spectrum (75.5 MHz, CDCl , ꢅ, ppm): 14.06, 14.54, 15.79, 18.39, 19.19, 20.21, 21.80, 22.55, 22.63,
3
24.84, 25.48, 28.22, 29.27, 29.29, 29.34, 29.36, 29.48, 29.53, 29.55, 29.60, 30.43, 31.86, 32.79,, 33.33, 36.80, 38.20, 40.63,
42.36, 42.44, 42.76, 44.72, 46.86, 49.15, 51.26, 51.43, 56.47, 109.83 (C-29), 118.25 (C-2), 150.20 (C-20), 154.44 (C-3),
176.22 (CONH), 176.57 (C-28).
Pentadecanoylhydrazone of 2,3-seco-28-methoxycarbonyl-1-cyanolup-20(29)-en-3-al (3d), C H N O . Yield
46 77
3 3
21
after purification by CC, 0.32 g (44%), R 0.44 (hexane:EtOAc, 10:1), yellow paste, [ꢁ] +3.1° (c 0.5, CHCl ). IR spectrum
f
D
3
–1
(ꢃ, cm ): 1670 (CH=NNHCO), 1730 (COOCH ), 2242 (CꢄN), 3202 (NH).
3
PMR spectrum (300 MHz, CDCl , ꢅ, ppm, J/Hz): 0.85 (3H, t, J = 6.9, CH ), 0.90, 0.93, 1.00, 1.16, 1.18 (5 ꢆ 3H, 5s,
3
3
5CH ), 1.67 (3H, s, CH -30), 2.26 and 2.56 (2H, 2d, J = 18.2, H -1, AB-system), 2.99 (1H, td, J = 11.1, 5.7, H-19), 3.66
3
3
AB
2
(3H, s, COOCH ), 4.60 and 4.72 (2H, 2s, H -29), 7.18 (3H, s, CH-3), 9.08 (1H, br.s, NH).
3
2
13
C NMR spectrum (75.5 MHz, CDCl , ꢅ, ppm): 14.07, 14.55, 15.81, 18.41, 19.20, 20.20, 21.80, 22.55, 22.65,
3
24.84, 25.49, 28.23, 29.32 (2C), 29.34 (2C), 29.37, 29.49, 29.60 (2C), 29.61 (2C), 29.65 (2C), 30.44, 31.88, 32.81, 33.36,
36.81, 38.21, 40.64, 42.37, 42.45, 42.77, 44.74, 46.86, 49.16, 51.26, 51.45, 56.48, 109.83 (C-29), 118.26 (C-2), 150.20
(C-20), 154.39 (C-3), 176.17 (CONH), 176.57 (C-28).
Benzoylhydrazone of 2,3-seco-28-methoxycarbonyl-1-cyanolup-20(29)-en-3-al (3e), C H N O . Yield after
38 53
3 3
21
purification by CC, 0.24 g (68%), R 0.26 (hexane:EtOAc, 5:1), mp 128–131°C (hexane:EtOAc, 10:1), [ꢁ] +4.2° (c 0.5,
f
D
–1
CHCl ). IR spectrum (ꢃ, cm ): 1653 (CH=NNHCO), 1726 (COOCH ), 2233 (CꢄN), 3236 (NH).
3
3
PMR spectrum (300 MHz, CDCl , ꢅ, ppm, J/Hz): 0.91 (2 ꢆ 3H, s, 2CH ), 0.99, 1.18, 1.25 (3 ꢆ 3H, 3s, 3CH ), 1.67
3
3
3
(3H, s, CH -30), 2.25 and 2.54 (2H, 2d, J
= 18.2, H -1, AB-system), 2.99 (1H, td, J = 10.7, 5.1, H-19), 3.66 (3H, s,
3
AB
2
COOCH ), 4.60 and 4.72 (2H, 2s, H -29), 7.42 (2H, t, J = 7.2, arom.), 7.50 (1H, t, J = 7.2, arom.), 7.70 (1H, s, H-3), 7.84 (2H,
3
2
d, J = 6.9, arom.), 9.32 (1H, br.s, NH).
13
C NMR spectrum (75.5 MHz, CDCl , ꢅ, ppm): 14.54, 15.79, 18.56, 19.21, 19.71, 21.63, 25.40, 28.50, 29.46,
3
29.57, 30.43, 31.89, 33.47, 36.81, 38.10, 40.63, 42.49, 42.73 (2C), 44.88, 46.84, 49.15, 51.28, 51.55, 56.46, 109.81 (C-29),
118.79 (C-2), 127.29 (2C arom.), 128.62 (2C arom.), 131.82 (arom.), 133.21 (arom.), 150.23 (C-20), 160.38 (C-3), 163.62
(CONH), 176.54 (C-28).
Acetylhydrazone of 1-cyano-2,3-seco-19ꢀ,28-epoxy-18ꢁ-olean-3-al (4a), C H N O . Yield 0.23 g (45%),
32 51
3 2
21
–1
R 0.12 (CHCl :EtOAc, 10:1), mp 65–67°C (CHCl :EtOAc, 10:1), [ꢁ] +30.0° (c 0.5, CHCl ). IR spectrum (ꢃ, cm ): 1676
f
3
3
D
3
(CH=N), 2240 (CꢄN), 3208 (NH).
PMR spectrum (300 MHz, CDCl , ꢅ, ppm, J/Hz): 0.78, 0.92, 0.95, 0.97, 1.17, 1.19, 1.24 (7 ꢆ 3H, 7s, 7CH ), 2.23
3
3
(3H, s, CH ), 2.32 and 2.60 (2H, 2d, J = 18.2, H -1, AB-system), 3.44 and 3.75 (2H, 2d, J = 7.8, H -28, AB-system), 3.52
3
AB
2
AB
2
(1H, s, H-19), 7.19 (1H, s, H-3), 8.87 (1H, br.s, NH).
13
C NMR spectrum (75.5 MHz, CDCl , ꢅ, ppm): 13.39, 15.70, 18.73, 20.17, 20.31, 21.88, 22.59, 24.50, 26.13,
3
26.35, 26.42, 28.18, 28.76, 29.85, 32.64, 32.88, 34.27, 36.24, 36.61, 40.55, 41.10, 41.45, 42.36, 42.51, 45.25, 46.58, 51.61,
71.23 (C-28), 87.83 (C-19), 118.28 (C-2), 154.61 (C-3), 173.37 (CONH).
2-Ethylpentanoylhydrazone of 1-cyano-2,3-seco-19ꢀ,28-epoxy-18ꢁ-olean-3-al (4b), C H N O . Yield 0.12 g
38 63
3 2
21
–1
(20%), R 0.4 (CHCl :EtOAc, 10:1), mp 73–75°C (CHCl :EtOAc, 10:1), [ꢁ] +18.6° (c 0.5, CHCl ). IR spectrum (ꢃ, cm ):
f
3
3
D
3
1668 (CH=N), 2244 (CꢄN), 3204 (NH).
PMR spectrum (300 MHz, CDCl , ꢅ, ppm, J/Hz): 0.78, 0.95, 0.97, 1.18, 1.19 (5 ꢆ 3H, 5s, 5CH ), 0.86 and 0.88
3
3
(2 ꢆ 3H, 2t, J = 6.6, 2CH ), 0.92 (2 ꢆ 3H, s, 2CH ), 2.30 and 2.58 (2H, 2d, J = 17.7, H -1, AB-system), 3.02–3.22 (1H, m,
3
3
AB
2
=NNHCOCH(C H )C H ), 3.44 and 3.75 (2H, 2d, J = 7.8, H -28, AB-system), 3.52 (1H, s, H-19), 7.15 (1H, s, H-3), 8.54
2
5
4
9
AB
2
(1H, br.s, NH).
13
C NMR spectrum (75.5 MHz, CDCl , ꢅ, ppm): 12.03, 13.38, 13.98, 15.67, 18.60, 20.13, 21.87, 22.65, 22.69,
3
24.48, 26.11, 26.32, 26.40, 28.34, 28.73, 29.62, 29.76, 31.68, 31.79, 32.62, 32.85, 34.24, 36.21, 36.59, 40.51, 41.07, 41.42,
42.41, 42.46, 42.54, 45.16, 46.54, 51.51, 71.20 (C-28), 87.81 (C-19), 118.23 (C-2), 154.28 (C-3), 178.97 (CONH).
Undecanoylhydrazone of 1-cyano-2,3-seco-19ꢀ,28-epoxy-18ꢁ-olean-3-al (4c), C H N O . Yield 0.32 g (50%),
41 69
3 2
21
–1
R 0.34 (CHCl :EtOAc, 10:1), mp 143–145°C (CHCl :EtOAc, 10:1), [ꢁ] +22.9° (c 0.5, CHCl ). IR spectrum (ꢃ, cm ):
f
3
3
D
3
1682 (CH=N), 2242 (CꢄN), 3196 (NH).
PMR spectrum (300 MHz, CDCl , ꢅ, ppm, J/Hz): 0.78, 0.95, 0.97, 1.17, 1.19 (5 ꢆ 3H, 5s, 5CH ), 0.86 (3H, t, J = 6.6,
3
3
CH ), 0.92 (2 ꢆ 3H, s, 2CH ), 2.31 and 2.59 (1H, d, J = 18.3, H-1), 2.58 (2H, t, J = 7.5, COCH (CH ) CH ), 3.44 and 3.75
3
3
AB
2
2 9
3
(2H, 2d, J = 7.7, H -28, AB-system), 3.52 (1H, s, H-19), 7.16 (1H, s, H-3), 8.67 (1H br.s, NH).
AB
2
41