10866
A. Ranise et al. / Tetrahedron 69 (2013) 10858e10868
198e200 ꢁC (ethanol); [Found: C, 64.25; H, 4.67; N, 4.07; S, 8.91.
19H17NO4S requires C, 64.21; H, 4.82; N, 3.94; S, 9.02%]; nmax
(CHCl3): 3454, 1713, 1577, 1306, 1148 cmꢀ1
dH (300 MHz, CDCl3) d:
2.24 (s, 3H, CH3), 3.62 (s, 3H, OCH3), 7.00e7.19 (m, 4H, AreH),
7.41e7.53 (m, 3H, AreH), 7.92e7.97 (m, 2H, AreH), 8.27 (s, 1H, CH]
C), 8.93 (br s, 1H, NH); dC (75.5 MHz, DMSO-d6): 12.2, 52.0, 106.8,
111.8, 119.3, 121.1, 122.3, 123.3, 125.3, 127.5, 129.1, 133.1, 136.1, 139.6,
141.5, 146.5, 164.2. 3JC,H¼11.0 Hz (CO).
1.24e1.29 (m, 12H, 4CH3), 4.51e4.71 (m, 2H, 2CH), 7.20e7.33 (m,
2H, AreH), 7.51e7.57 (m, 6H, AreH), 7.90 (d, JH,P¼20.6 Hz, 1H, CH]
C), 8.07e8.16 (m, 1H, indole H-4), 12.72 (br s, 1H, NH); dC (75.5 MHz,
DMSO-d6): 23.4e23.5 (3JC,P¼4.87 Hz), 23.5e23.6 (3JC,P¼4.87 Hz),
71.3e71.4 (2JC,P¼5.47 Hz), 91.5e94.1 (JC,P¼199.2 Hz), 108.4e108.6
(3JC,P¼18.6 Hz), 112.5, 117.7e117.8 (2JC,P¼11.6 Hz), 121.4, 121.9, 123.5,
124.8, 128.9, 129.8, 130.0, 136.8, 146.7, 152.4e152.5 (2JC,P¼8.55 Hz).
C
;
4.3.21. (2E)-2-(Methylsulfonyl)-3-(2-phenyl-1H-indol-3-yl)acryloni-
trile (13i). Yellow crystalline solid (2.51 g, 78%); mp: 220e222 ꢁC
(ethanol); [Found: C, 67.21; H, 4.12; N, 8.73; S, 9.59. C18H14N2O2S
requires C, 67.06; H, 4.38; N, 8.69; S, 9.95%]; nmax (KBr): 3319, 2207,
4.3.14. [(2-Phenyl-1H-indol-3-y)lmethylene]malononitrile
(13a). Yellow crystalline solid (1.99 g, 74%); mp: 225e227 ꢁC
(ethanol) (lit.11: 210 ꢁC ethanol; lit.6: 217e219 ꢁC); dC (75.5 MHz,
DMSO-d6): 72.4, 108.5, 112.8, 115.6, 116.4, 122.1, 124.2, 124.5, 129.1,
129.4, 130.0, 130.2, 137.1, 148.9, 154.4. 3JC,H¼13.6 Hz (CNtrans); 8.1 Hz
(CNcis).
1562, 1313, 1136 cmꢀ1
; dH (300 MHz, DMSO-d6): 3.25 (s, 3H, CH3),
7.25e7.30 (m, 2H, AreH), 7.49e7.58 (m, 6H, AreH), 8.03 (s,1H, CH]
C), 8.17e8.22 (m, 1H, indole H-4), 12.96 (br s, 1H, NH); dC (75.5 MHz,
DMSO-d6): 42.5, 104.0, 106.5, 112.8, 115.9, 122.1, 122.2, 124.1, 124.7,
129.1, 129.4, 130.1, 130.3, 137.2, 147.2, 149.8. 3JC,H¼12.9 Hz (CN).
4.3.15. (2E)-2-(2,2-Dimethylpropanoyl)-3-(2-phenyl-1H-indol-3-yl)
acrylonitrile (13b). Orange crystalline solid (1.67 g, 51%); mp:
211e213 ꢁC (ethanol); [Found: C, 80.47; H, 6.42; N, 8.46. C22H20N2O
requires C, 80.46; H, 6.14; N, 8.53%]; nmax (KBr): 3350, 2971, 2206,
4.3.22. (2E)-3-(2-Phenyl-1H-indol-3-yl)-2-(phenylsulfonyl)acryloni-
trile (13j). Yellow crystalline solid (2.64 g, 69%); mp: 182e184 ꢁC
(ethanol); [Found: C, 71.51; H, 4.52; N, 7.45; S, 7.95. C23H16N2O2S
requires C, 71.86; H, 4.19; N, 7.29; S, 8.34%]; nmax (KBr): 3493, 2205,
1672, 1543 cmꢀ1
; dH (300 MHz, DMSO-d6): 1.39 (s, 9H, 3CH3),
7.29e7.39 (m, 2H, arom. H), 7.55e7.62 (m, 6H, arom. H), 8.11e8.16
(m, 1H, H-4), 8.44 (s, 1H, CH]C), 12.90 (br s, 1H, NH); dC (75.5 MHz,
1567, 1315, 1146 cmꢀ1
; dH (300 MHz, CDCl3): 7.20e7.25 (m, 2H,
DMSO-d6)
d
: 26.3, 43.5, 100.1, 108.4, 112.5, 120.2, 121.5, 122.8, 123.7,
indole H-5, H-6), 7.36e7.60 (m, 9H, AreH), 7.89e7.94 (m, 2H,
AreH), 8.10e8.17 (m, 1H, indole H-4), 8.27 (s, 1H, CH]C), 9.77 (br s,
1H, NH); dC (75.5 MHz, DMSO-d6): 104.0, 107.0, 113.0, 115.7, 122.1,
122.3, 124.3, 124.7, 127.3, 129.1, 129.3, 130.0, 130.2, 130.5, 134.2,
137.3, 139.5, 147.0, 150.6.
124.7, 128.9, 129.0, 130.0, 137.1, 148.6, 151.5, 197.8.
4.3.16. Ethyl
(2E)-2-cyano-3-(2-phenyl-1H-indol-3-yl)acrylate
(13c). Yellow crystalline solid (2.88 g, 91%); mp: 218e220 ꢁC
(ethanol) (lit.7: 219 ꢁC, ethanol; lit.11: 219e220 ꢁC, ethanol/H2O); dC
(75.5 MHz, DMSO-d6): 14.1, 61.5, 94.4, 107.9, 112.6, 117.7, 121.6,
122.5, 123.8, 124.8, 129.0, 129.8, 130.0, 137.1, 148.6, 149.6, 163.7.
3JC,H¼13.2 Hz (CN); 6.6 Hz (CO).
4.3.23. 3-[(2-Phenyl-1H-indol-3-yl)methylene]pentane-2,4-dione
(13k). Yellow crystalline solid (1.27 g, 42%); mp: 198e200 ꢁC (ac-
etone/ethyl acetate); [Found: C, 79.28; H, 6.03; N, 4.59. C20H17NO2
requires C, 79.19; H, 5.65; N, 4.62%]; nmax (KBr): 3239, 1703,
4.3.17. (2E)-2-Cyano-3-(2-phenyl-1H-indol-3-yl)acrylamide
(13d). Yellow crystalline solid (1.56 g, 55%); mp: 292e294 ꢁC (DMF)
(lit.7: 292 ꢁC, ethanol/pyridine); dC (75.5 MHz, DMSO-d6): 100.9,
107.2, 112.3, 118.2, 120.9, 121.9, 123.2, 125.0, 128.9, 129.5, 129.6,
130.3, 136.8, 145.3, 146.3, 163.8. 3JC,H¼13.5 Hz (CN); 6.2 Hz (CO).
1569 cmꢀ1
; dH (300 MHz, DMSO-d6): 2.14 (s, 3H, CH3), 2.29 (s, 3H,
CH3), 7.04e7.32 (m, 4H, AreH), 7.45e7.62 (m, 5H, AreH), 7.78 (s, 1H,
CH]C), 12.33 (br s, 1H, NH); dC (75.5 MHz, DMSO-d6): 27.3, 31.0,
107.4, 112.2,119.7, 120.8,122.9, 126.1, 128.9, 129.1, 129.3,130.8, 136.7,
137.4, 137.9, 142.6, 195.8, 204.7.
4.3.18. (2E)-3-(2-Phenyl-1H-indol-3-yl)-2-(piperidin-1-ylcarbonyl)
acrylonitrile (13e). Pale yellow crystalline solid (2.13 g, 60%); mp:
233e234 ꢁC (ethanol). [Found: C, 77.99; H, 6.29; N, 12.06.
4.3.24. Ethyl
(2Z)-2-acetyl-3-(2-phenyl-1H-indol-3-yl)acrylate
(13l). Yellow crystalline solid (1.50 g, 45%); mp: 173e174 ꢁC (eth-
anol); [Found: C, 75.35; H, 5.89; N, 4.06. C21H19NO3 requires C,
75.66; H, 5.74; N, 4.20%]; nmax (KBr): 3268, 1723, 1635, 1572, 1246,
C
23H21N3O requires C, 77.72; H, 5.96; N, 11.82%]; nmax (KBr): 3280,
2942, 2202, 1609, 1575 cmꢀ1
;
dH (300 MHz, DMSO-d6) : 1.48e1.68
d
1211 cmꢀ1
;
dH (300 MHz, DMSO-d6): 0.99 (t, J¼7.1 Hz, 3H, CH3), 2.30
(m, 6H, 3CH2), 3.52e3.64 (m, 4H, 2CH2), 7.24e7.35 (m, 2H, arom. H),
7.52e7.66 (m, 6H, arom. H), 7.84 (s, 1H, CH]C), 8.01e8.06 (m, 1H),
12.53 (br s, 1H, NH); dC (75.5 MHz, DMSO-d6): 23.8, 25.4, 45.3e46.3
(very broad signal),101.2,107.1,112.2,117.8,120.8,121.6,123.1,125.0,
128.9, 129.4, 130.4, 136.7, 144.3, 145.8, 163.4.
(s, 3H, CH3), 4.05 (q, J¼7.1 Hz, 2H, CH2), 7.10e7.24 (m, 4H, AreH),
7.36e7.57 (m, 5H, AreH), 7.79 (s, 1H, CH]C), 12.30 (br s, 1H, NH); dC
(75.5 MHz, DMSO-d6): 13.6, 27.1, 60.6, 107.7, 112.2, 119.8, 120.8,
122.9, 125.8, 128.9, 129.1, 129.4, 130.7, 136.6, 138.4, 143.5, 168.0,
3
194.6. JC,H¼11.8 Hz (COOEt); 6.6 Hz (COMe).
4.3.19. (2E)-N-(4-Chlorophenyl)-2-cyano-3-(2-phenyl-1H-indol-3-
yl)acrylamide (13f). Yellow crystalline solid (2.46 g, 62%); mp:
217e219 ꢁC (acetone); [Found: C, 72.68; H, 4.40; N, 10.88.
4.3.25. (2Z)-1-Phenyl-2-[(2-phenyl-1H-indol-3-yl)methylene]bu-
tane-1,3-dione (13m). Yellow crystalline solid (1.46 g, 40%); mp:
216e217 ꢁC (ethanol); [Found: C, 81.91; H, 5.28; N, 3.79. C25H19NO2
requires C, 82.17; H, 5.24; N, 3.83%]; nmax (KBr): 3283, 1665, 1624,
C
24H16ClN3O requires C, 72.45; H, 4.05; N,10.56%]; nmax (KBr): 3394,
3302, 2212, 1648, 1560 cmꢀ1
;
dH (300 MHz, DMSO-d6): 7.27e7.39
1570 cmꢀ1
; dH (300 MHz, DMSO-d6): 2.30 (s, 3H, CH3), 6.81e6.90
(m, 4H, arom. H), 7.54e7.71 (m, 8H, arom. H), 8.04e8.10 (m, 1H, H-
4), 8.30 (s, 1H, CH]C), 10.18 (s, 1H, CONH) 12.71 (br s, 1H, NH); dC
(75.5 MHz, DMSO-d6): 101.0, 107.3, 112.4, 117.7, 121.1, 122.0, 122.2,
123.4, 125.0, 127.6, 128.4, 129.0, 129.7, 130.2, 136.9, 137.5, 145.9,
146.8, 161.6.
(m, 1H, AreH), 6.98e7.10 (m, 1H, AreH), 7.20e7.64 (m, 10H, AreH),
7.77e7.83 (m, 2H, AreH), 7.96 (s, 1H, CH]C), 12.20 (br s, 1H, NH); dC
(75.5 MHz, DMSO-d6): 27.0, 107.7, 112.0, 120.5, 120.5, 122.7, 125.5,
128.5, 128.8, 128.9, 129.1, 129.5, 130.7, 133.2, 134.6, 136.6, 137.4,
138.2, 143.5, 196.4, 198.3.
4.3.20. Diisopropyl
(E)-1-cyano-2-(2-phenyl-1H-indol-3-yl)vinyl-
4.3.26. Methyl (2E)-3-(2-phenyl-1H-indol-3-yl)-2-(phenylsulfonyl)
acrylate (13n). Yellow crystalline solid (1.75 g, 42%); mp:
176e178 ꢁC (ethanol/diethyl ether); [Found: C, 68.82; H, 4.71; N,
3.12; S, 7.37. C24H19NO4S requires C, 69.05; H, 4.59; N, 3.36; S,
phosphonate (13h). Yellow crystalline solid (1.47 g, 36%); mp:
195e196 ꢁC (ethyl acetate); [Found: C, 67.80; H, 6.54; N, 6.77.
C
23H25N2O3P requires C, 67.64; H, 6.17; N, 6.86%]; nmax (KBr): 3163,
2981, 2203, 1577, 1250, 1050 cmꢀ1
;
dH (300 MHz, DMSO-d6):
7.68%]; nmax (CHCl3): 3449, 1714, 1577, 1308, 1149 cmꢀ1
; dH