RSC Advances
Paper
Me), 0.97 (3H, s, Me), 0.96 (3H, s, Me), 0.93 (3H, s, Me), 0.92 (3H, 39.2, 37.8, 34.2, 33.8, 33.0, 32.3, 31.4, 30.7, 29.7, 27.7, 25.6, 24.1,
s, Me); 13C NMR (125 MHz, CDCl3): d 190.5, 175.5, 151.8, 144.4, 23.7, 23.5, 23.0, 19.1, 17.5, 11.5; EI MS: m/z 647 ([M]+, 3), 406
143.4, 142.0, 138.2, 137.9, 133.4, 132.7, 128.6 (C ꢃ 2 in Ph), (100), 248 (16), 203 (38), 189 (13), 69 (11), 55 (9); HREIMS m/z
128.5 (C ꢃ 2 in Ph), 123.4, 123.0, 122.0, 121.3, 121.4, 111.8, 55.9, 647.3946 (calcd for C43H53NO4, 647.3917).
52.0, 47.4, 46.1, 45.9, 42.0, 41.6, 40.7, 39.6, 36.2, 34.4, 33.9, 33.1,
{4-[(E)-3-(Thiophen-2-yl)acryloyl]phenyl}-3-cyano-3,4-seco-4-
32.3 (C ꢃ 2), 31.8, 30.7, 27.7, 25.6, 23.6, 23.3, 23.1, 22.8, 19.5, yliden-olean-12-en-28-oate (5d). Yellow solid, yield 32.3%, m.p.
17.1, 15.6; EI MS: m/z 674 ([M]+, 1), 407 (10), 393 (100), 203 (28), 149.1–150.8 ꢁC; IR (KBr): 2244 (CN), 1749 (–COO–), 1660 (C]O)
189 (32), 95 (24), 69 (10); HREIMS m/z 674.4310 (calcd for cmꢂ1; 1H NMR (400 MHz, CDCl3): d 8.03 (2H, d, J ¼ 8.4 Hz, Ar-
C
46H58O4, 674.4285).
H), 7.95 (1H, d, J ¼ 16.0 Hz, H-90), 7.43 (1H, s, H-500), 7.36 (1H, d,
{4-[(E)-3-(4-Methoxyphenyl)acryloyl]phenyl}-3-cyano-3,4-seco- J ¼ 3.6 Hz, H-300), 7.31 (1H, d, J ¼ 16.4 Hz, H-80), 7.16 (2H, d, J ¼
4-yliden-olean-12-en-28-oate (5a). Straw yellow solid, yield 8.4 Hz, Ar-H), 7.08 (1H, t, J ¼ 3.6 Hz, H-400), 5.38 (1H, s, H-12),
31.4%, m.p. 133.3–134.0 ꢁC; IR (KBr): 2244 (CN), 1748 (–COO–), 4.90 (1H, s, H2-24), 4.66 (1H, s, H2-24), 3.01 (1H, dd, J1 ¼ 3.6 Hz,
1660 (C]O) cmꢂ1; 1H NMR (400 MHz, CDCl3): d 8.03 (2H, d, J ¼ J2 ¼ 13.6 Hz, H-18), 1.73 (3H, s, Me), 1.20 (3H, s, Me), 0.98 (3H,
8.0 Hz, Ar-H), 7.79 (1H, d, J ¼ 16.0 Hz, H-90), 7.59 (2H, d, J ¼ 8.4 s, Me), 0.94 (3H, s, Me), 0.93 (3H, s, Me), 0.90 (3H, s, Me); 13C
Hz, Ar-H), 7.39 (1H, d, J ¼ 16.0 Hz, H-80), 7.15 (2H, d, J ¼ 8.4 Hz, NMR (125 MHz, CDCl3): d 188.6, 175.7, 154.6, 146.7, 143.4,
Ar-H), 6.94 (2H, d, J ¼ 8.4 Hz, Ar-H), 5.39 (1H, s, H-12), 4.90 (1H, 140.3, 137.4, 135.4, 132.2, 129.9 (C ꢃ 2 in Ph), 128.9, 128.4,
s, H2-24), 4.66 (1H, s, H2-24), 3.85 (3H, s, –OMe) 3.02 (1H, dd, 122.3, 121.8 (C ꢃ 2 in Ph), 120.5, 120.2, 114.2, 50.6, 47.2, 45.6,
J1 ¼ 3.6 Hz, J2 ¼ 13.6 Hz, H-18), 1.74 (3H, s, Me), 1.21 (3H, s, Me), 42.3, 41.5, 39.4, 39.2, 37.8, 34.4, 33.8, 33.0, 32.3, 31.4, 30.7,
0.98 (3H, s, Me), 0.95 (3H, s, Me), 0.93 (3H, s, Me), 0.90 (3H, s, 29.7, 27.7, 25.6, 24.1, 23.7, 23.5, 23.0, 19.1, 17.5, 11.5; EI MS: m/
Me); 13C NMR (125 MHz, CDCl3): d 189.3, 175.7, 161.7, 154.6, z 663 ([M]+, 8), 406 (100), 248 (34), 203 (43), 189 (11), 69 (9), 55
146.7, 144.9, 143.4, 135.8, 130.2 (C ꢃ 2 in Ph), 129.9 (C ꢃ 2 in (7); HREIMS m/z 663.3757 (calcd for C43H53NSO3, 663.3768).
Ph), 127.5, 122.3, 121.7 (C ꢃ 2 in Ph), 120.2, 119.5, 114.4 (C ꢃ 2
{4-[(E)-3-Oxo-3-phenylprop-1-enyl]phenyl}-3-cyano-3,4-seco-
in Ph), 114.2, 55.4, 50.6, 47.2, 45.6, 42.3, 41.5, 39.4, 39.2, 37.8, 4-yliden-olean-12-en-28-oate (5e). Straw yellow solid, yield
34.3, 33.8, 33.0, 32.3, 31.4, 30.7, 29.7, 27.7, 25.6, 24.1, 23.7, 23.5, 33.6%, m.p. 147.2–148.1 ꢁC; IR (KBr): 2245 (CN), 1748 (–COO–),
23.0, 19.1, 17.5, 11.5; EI MS: m/z 688 ([M + 1]+, 4), 687 ([M]+, 5), 1667 (C]O) cmꢂ1; 1H NMR (400 MHz, CDCl3): d 8.01 (2H, d, J ¼
406 (82), 248 (58), 203 (100), 189 (85), 69 (48), 57 (55); HREIMS 8.0 Hz, Ar-H), 7.80 (1H, d, J ¼ 16.0 Hz, H-90), 7.65 (2H, d, J ¼ 8.0
m/z 687.4271 (calcd for C46H57NO4, 687.4254).
Hz, Ar-H), 7.57 (1H, d, J ¼ 15.6 Hz, H-80), 7.48 (3H, m, Ar-H), 7.09
{4-Cinnamoylphenyl}-3-cyano-3,4-seco-4-yliden-olean-12-en- (2H, d, J ¼ 8.0 Hz, Ar-H), 5.37 (1H, s, H-12), 4.90 (1H, s, H2-24),
28-oate (5b). Straw yellow solid, yield 45.6%, m.p. 131.1– 4.66 (1H, s, H2-24), 3.01 (1H, dd, J1 ¼ 3.6 Hz, J2 ¼ 14.0 Hz, H-18),
132.5 ꢁC; IR (KBr): 2245 (CN), 1750 (–COO–), 1665 (C]O) cmꢂ1
;
1.74 (3H, s, Me), 1.21 (3H, s, Me), 0.98 (3H, s, Me), 0.95 (3H, s,
1H NMR (400 MHz, CDCl3): d 8.06 (2H, d, J ¼ 8.0 Hz, Ar-H), 7.82 Me), 0.93 (3H, s, Me), 0.91 (3H, s, Me); 13C NMR (125 MHz,
(1H, d, J ¼ 15.6 Hz, H-90), 7.62 (2H, d, J ¼ 8.4 Hz, Ar-H), 7.52 (1H, CDCl3): d 190.3, 175.9, 152.8, 146.7, 143.8, 143.4, 138.1, 132.3,
d, J ¼ 15.6 Hz, H-80), 7.42 (3H, m, Ar-H), 7.17 (2H, d, J ¼ 8.0 Hz, 132.8, 139.5 (C ꢃ 2 in Ph), 128.6 (C ꢃ 2 in Ph), 128.5 (C ꢃ 2 in
Ar-H), 5.38 (1H, s, H-12), 4.90 (1H, s, H2-24), 4.66 (1H, s, H2-24), Ph), 122.3, 122.2 (C ꢃ 2 in Ph), 121.9, 120.2, 114.2, 50.6, 47.2,
3.01 (1H, dd, J1 ¼ 3.6 Hz, J2 ¼ 14.0 Hz, H-18), 1.74 (3H, s, Me), 45.6, 42.3, 41.5, 39.4, 39.2, 37.8, 34.3, 33.8, 33.0, 32.3, 31.4, 30.7,
1.21 (3H, s, Me), 0.98 (3H, s, Me), 0.95 (3H, s, Me), 0.93 (3H, s, 29.7, 27.7, 25.6, 24.1, 23.7, 23.6, 23.0, 19.1, 17.5, 11.5; EI MS: m/z
Me), 0.90 (3H, s, Me); 13C NMR (125 MHz, CDCl3): d 189.7, 176.1, 657 ([M]+, 1), 406 (100), 248 (8), 203 (17), 189 (8), 69 (7), 55 (6);
155.1, 147.1, 145.4, 143.8, 135.9, 135.2, 131.1, 130.5 (C ꢃ 2 in HREIMS m/z 657.4175 (calcd for C45H55NO3, 657.4168).
Ph), 129.4 (C ꢃ 2 in Ph), 128.9 (C ꢃ 2 in Ph), 122.8, 122.2 (C ꢃ 2
{4-[(E)-3-(4-Methoxyphenyl)acryloyl]phenyl}-3,4-seco-4-yliden-
in Ph), 121.7, 120.6, 114.6, 51.1, 47.2, 46.0, 42.7, 41.9, 39.9, 39.7, 12-oxo-olean-28-methoxycarbonyl-3-oate (6a). Straw yellow
38.2, 34.7, 34.2, 33.5, 32.7, 31.8, 31.2, 30.1, 27.7, 26.1, 24.5, 24.1, solid, yield 32.7%, m.p. 142.7–143.5 ꢁC; IR (KBr): 1761 (–COO–),
24.0, 23.4, 19.5, 17.9, 12.0; EI MS: m/z 657 ([M]+, 3), 406 (63), 248 1721 (–COO–), 1661 (C]O) cmꢂ1; 1H NMR (500 MHz, CDCl3): d
(78), 203 (100), 189 (21), 69 (54), 57 (44); HREIMS m/z 657.4190 8.00 (2H, d, J ¼ 8.5 Hz, Ar-H), 7.74 (1H, d, J ¼ 15.5 Hz, H-90), 7.55
(calcd for C45H55NO3, 657.4198).
(2H, d, J ¼ 8.5 Hz, Ar-H), 7.36 (1H, d, J ¼ 16.0 Hz, H-80), 7.17 (2H,
{4-[(E)-3-(Furan-2-yl)acryloyl]phenyl}-3-cyano-3,4-seco-4-yliden- d, J ¼ 8.5 Hz, Ar-H), 6.88 (2H, d, J ¼ 8.5 Hz, Ar-H), 4.87 (1H, s, H2-
olean-12-en-28-oate (5c). Yellow solid, yield 29.6%, m.p. 173.6– 24), 4.69 (1H, s, H2-24), 3.77 (3H, s, –OMe), 3.64 (3H, s, –OMe),
174.5 ꢁC; IR (KBr): 2244 (CN), 1748 (–COO–), 1679 (C]O) cmꢂ1
;
2.76 (1H, dd, J1 ¼ 4.0 Hz, J2 ¼ 13.5 Hz, H-18), 2.63 (2H, m, H-2),
1H NMR (400 MHz, CDCl3): d 8.07 (2H, d, J ¼ 8.0 Hz, Ar-H), 7.61 1.72 (3H, s, Me), 0.97 (3H, s, Me), 0.95 (3H, s, Me), 0.93 (3H, s,
(1H, d, J ¼ 15.6 Hz, H-90), 7.53 (1H, s, H-500), 7.44 (1H, d, J ¼ 15.6 Me), 0.86 (3H, s, Me), 0.84 (3H, s, Me); 13C NMR (125 MHz,
Hz, H-80), 7.16 (2H, d, J ¼ 8.4 Hz, Ar-H), 6.73 (1H, d, J ¼ 4.0 Hz, CDCl3): d 210.8, 188.8, 178.0, 171.1, 161.5, 153.7, 146.3, 135.7,
H-300), 6.52 (1H, t, J ¼ 1.6 Hz, H-400), 5.38 (1H, s, H-12), 4.90 (1H, 127.2, 144.6, 130.1 (C ꢃ 2 in Ph), 129.7 (C ꢃ 2 in Ph), 121.4 (C ꢃ
s, H2-24), 4.66 (1H, s, H2-24), 3.01 (1H, dd, J1 ¼ 4.0 Hz, J2 ¼ 14.0 2 in Ph), 124.2 (C ꢃ 2 in Ph), 119.1, 113.9, 55.2, 51.6, 51.3, 49.8,
Hz, H-18), 1.73 (3H, s, Me), 1.20 (3H, s, Me), 0.98 (3H, s, Me), 47.0, 42.2, 40.8, 40.5, 38.7, 38.5, 36.0, 34.1, 33.2, 32.9, 32.6, 31.7,
0.94 (3H, s, Me), 0.93 (3H, s, Me), 0.89 (3H, s, Me); 13C NMR (125 30.4, 30.1, 28.1, 27.3, 24.1, 23.0 (C ꢃ 2), 22.5, 20.2, 18.8, 15.6; EI
MHz, CDCl3): d 188.6, 175.7, 154.7, 151.5, 146.7, 145.0, 143.4, MS: m/z 736 ([M]+, 1), 482 (29), 467 (69), 407 (65), 278 (40), 254
135.4, 130.8, 129.9 (C ꢃ 2 in Ph), 122.3, 121.8 (C ꢃ 2 in Ph), (100), 218 (38), 65 (8); HREIMS m/z 736.4358 (calcd for
120.2, 118.9, 116.5, 114.2, 112.7, 50.6, 47.2, 45.6, 42.3, 41.5, 39.4,
C47H60O7, 736.4377).
10872 | RSC Adv., 2014, 4, 10862–10874
This journal is © The Royal Society of Chemistry 2014