R. Chowdhury, S. K. Ghosh
FULL PAPER
2.6 Hz, 1 H, CHAHBS), 3.47 (dd, J = 12.6 and 12.6 Hz, 1 H,
8.8 Hz, 2 H, Ar) ppm. 13C NMR (50 MHz, CDCl3): δ = 55.4,
CHAHBS), 4.36 (dd, J = 12.6 and 2.6 Hz, 1 H, CHCH2S), 7.33 (s, 110.1, 114.2 (2 C), 117.9, 118.0, 126.1, 128.3, 128.5 (2 C), 128.7 (2
1 H, ArCH), 7.37–7.40 (m, 8 H, Ar), 7.72–7.78 (m, 2 H, Ar) ppm. C), 131.2 (2 C), 138.5, 144.1, 145.4, 161.4 ppm. ESI MS: m/z (%)
1H NMR (200 MHz, CDCl3): (polar isomer): δ = 2.63 (s, 3 H,
CH3S), 3.12–3.52 (m, 2 H, CH2S), 4.32 (dd, J = 5.0 and 10.4 Hz,
= 262 (18) [M+ + 1], 261 (100) [M+], 260 (52) [M+ – 1], 245 (17),
230 (55), 217 (25), 184 (46), 169 (17), 91 (36), 77 (28). GC: (200 °C –
1 H, CHCH2S), 7.17 (s, 1 H, ArCH), 7.35–7.41 (m, 8 H, Ar), 7.70– 10 °C/min – 260 °C – 5 °C/min – 300 °C) tR = 13.29 min (100%).
7.76 (m, 2 H, Ar) ppm. 13C NMR (50 MHz, CDCl3, mixture of
isomers): δ = 39.3, 45.5, 58.2, 58.8, 111.3, 112.9, 117.3, 117.7, 127.2,
127.8, 128.2, 128.4, 128.9, 129.1, 129.2, 129.3, 130.7, 130.8, 132.9,
137.9, 139.1, 144.8, 146.2 ppm.
C18H15NO (261.32): calcd. C 82.73, H 5.79, N 5.36; found C 82.41,
H 5.86, N 5.23.
(1Z)-2-Cyano-1-(3-bromophenyl)-3-phenyl-1,3-butadiene (5e): Yield
254 mg (82%) as thick gum. IR (neat): ν = 3019, 2935, 2221, 1593,
˜
(3RS,1E)-2-Cyano-1,3-diphenyl-3-ethoxy-1-propene (8b): Yield
1569, 1493, 1474, 1444, 1426, 1075, 914 cm–1. 1H NMR (200 MHz,
68 mg (26%) as viscous oil. IR (CHCl film): ν = 3019, 2975, 2836, CDCl3): δ = 5.50 (s, 1 H, C=CHAHB), 5.93 (s, 1 H, C=CHAHB),
˜
3
2216, 1600, 1561, 1488, 1268, 1098, 760 cm–1. 1H NMR (200 MHz,
CDCl3): δ = 1.30 (t, J = 7 Hz, 3 H, CH3CH2O), 3.43–3.74 (m, 2
H, CH3CHAHBO), 5.01 (s, 1 H, PhCHO), 7.22 (s, 1 H, ArCH),
7.27–7.48 (m, 8 H, Ar), 7.72–7.79 (m, 2 H, Ar) ppm. 13C NMR
(50 MHz, CDCl3): δ = 15.2, 65.0, 82.7, 113.6, 126.9 (2 C), 128.5,
128.7 (2 C), 128.8 (2 C), 129.1 (2 C), 133.1, 138.6, 143.0 ppm. EI
MS: m/z (%) = 264 (80) [M+ + H], 235 (82), 217 (98), 206 (50), 190
(97), 179 (92), 158 (55), 140 (98), 136 (93), 128 (100), 106 (99), 102
(100), 91 (48), 78 (98).
6.87 (s, 1 H, ArCH=C), 7.27–7.43 (m, 6 H, Ph and Ar), 7.51 (d, J
= 8 Hz, 1 H, Ar), 7.73 (s, 1 H, Ar), 7.79 (d, J = 8 Hz, 1 H, Ar)
ppm. 13C NMR (50 MHz, CDCl3): δ = 114.7, 116.8, 120.1, 122.8,
127.2, 128.6, 128.7 (4 C), 130.3, 132.4, 133.3, 135.4, 137.9, 142.6,
144.9 ppm. ESI MS: m/z (%) = 311 (6) [C17H1281BrN+], 309 (6)
[C17H1279BrN+], 230 (100), 202 (13), 101 (19), 77 (26). GC:
(200 °C – 10 °C/min – 260 °C – 5 °C/min – 300 °C) tR = 13.08 min
(100%). C17H12BrN (310.19): calcd. C 65.83, H 3.90, N 4.52; found
C 65.59, H 4.01, N 4.38.
(1Z,3E)-1-Cyano-2,4-diphenyl-1,3-butadiene (6b): Yield 30 mg (1Z)-2-Cyano-1-(2-methoxyphenyl)-3-phenyl-1,3-butadiene
(5f):
(13%). M.p. 57 °C. IR (CHCl ): ν = 3034, 2209, 1615, 1581, 1561,
Yield 198 mg (76%). M.p. 81–82 °C. IR (CHCl3 film): ν = 3019,
˜
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3
1491, 1449, 1375, 1199, 1071, 1005, 966, 803, 779, 753, 705, 690
cm–1. 1H NMR (200 MHz, CDCl3): δ = 5.55 (s, 1 H, CHCN), 6.59
(d, J = 16 Hz, 1 H, CH=CH-Ph), 7.04 (d, J = 16 Hz, 1 H, CH=CH-
Ph), 7.31–7.52 (m, 10 H, 2ϫPh) ppm. 13C NMR (50 MHz,
2219, 1599, 1491, 1466, 1437, 1251, 1179, 1027, 908 cm–1. 1H NMR
(200 MHz, CDCl3): δ = 3.75 (s, 3 H, OMe), 5.46 (s, 1 H,
C=CHAHB), 5.85 (s, 1 H, C=CHAHB), 6.86 (d, J = 8.4 Hz, 1 H,
Ar), 7.03 (t, J = 7.4 Hz, 1 H, Ar), 7.30–7.43 (m, 7 H, Ph, Ar and
CDCl3): δ = 97.4, 117.7, 127.3 (2 C), 128.1, 128.6 (2 C), 128.7 (2 ArCH=C), 8.06 (d, J = 7.4 Hz, 1 H, Ar) ppm. 13C NMR (50 MHz,
C), 128.8 (2 C), 129.3 (2 C), 135.0, 135.4, 139.8, 160.7 ppm. ESI CDCl3): δ = 55.5, 110.6, 113.1, 117.6, 118.5, 120.7, 122.8, 128.3,
MS: m/z (%) = 232 (2) [M+ + 1], 124 (100). GC: (260 °C isothermal) 128.4 (2 C), 128.6 (3 C), 131.8, 138.4, 140.3, 145.4, 157.7 ppm. EI
tR = 9.025 min (100%). HRMS: calcd. for C17H14N (M+ + H)
232.1126, found 232.1122. C17H13N (231.3): calcd. C 88.28, H 5.67,
N 6.06; found C 88.04, H 5.74, N 5.92.
MS: m/z (%) = 262 (44) [M+ + H], 261 (100) [M+], 246 (32), 230
(92), 219 (30), 218 (29), 202 (21), 184 (68), 169 (23), 108 (29), 91
(63), 77 (90), 63 (23). GC: (200 °C – 10 °C/min – 260 °C – 5 °C/
min – 300 °C) tR = 11.97 min (1.5%), tR = 12.21 min (98.5%).
HRMS: calcd. for C18H16NO (M+ + H) 262.1232, found 262.1237.
(1Z)-2-Cyano-1,3-diphenyl-1,3-butadiene (5b): Yield 190 mg (82%).
M.p. 51–52 °C. IR (CHCl ): ν = 3054, 2211, 1607, 1570, 1493,
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3
1445, 1209, 1100, 1072, 1029, 936, 908, 754, 682 cm–1. 1H NMR
(200 MHz, CDCl3): δ = 5.49 (s, 1 H, C=CHAHB), 5.92 (s, 1 H,
C=CHAHB), 6.99 (s, 1 H, PhCH=C), 7.30–7.43 (m, 8 H, Ar), 7.73–
7.78 (m, 2 H, Ar) ppm. 13C NMR (50 MHz, CDCl3): δ = 113.0,
117.4, 119.2, 128.4, 128.6 (2 C), 128.7 (2 C), 128.8 (2 C), 129.3 (2
C), 130.5, 133.4, 138.2, 144.6, 145.2 ppm. ESI MS: m/z (%) = 232
(1Z)-2-Cyano-1-(2-chlorophenyl)-3-phenyl-1,3-butadiene (5g): Yield
212 mg (80%). M.p. 62–63 °C. IR (CHCl3 film): ν = 3058, 3027,
˜
2925, 2222, 1612, 1588, 1574, 1493, 1466, 1441, 1053, 1036, 906,
762, 752 cm–1. 1H NMR (200 MHz, CDCl3): δ = 5.54 (s, 1 H,
C=CHAHB), 5.95 (s, 1 H, C=CHAHB), 7.30–7.46 (m, 9 H, Ph, Ar
and ArCH=C), 8.00–8.05 (m, 1 H, Ar) ppm. 13C NMR (50 MHz,
(60) [M+ + 1], 148 (100). GC: (260 °C isothermal) tR = 7.642 min CDCl3): δ = 116.1, 116.6, 120.1, 127.1, 128.5 (2 C), 128.6 (4 C),
(100%). C17H13N (231.3): calcd. C 88.28, H 5.67, N 6.06; found C
88.11, H 5.82, N 5.80.
129.4, 129.7, 131.2, 134.7, 137.8, 141.4, 144.9 ppm. ESI MS: m/z
(%) = 288 (12) [M+ + Na], 266 (100) [M+ + H], 154 (7). GC:
(200 °C–10 °C/min – 260 °C–5 °C/min – 300 °C) tR = 11.72 min
(100%). HRMS: calcd. for C17H13ClN (M+ + H) 266.0737, found
266.0740.
(1Z)-2-Cyano-1-(3-methoxyphenyl)-3-phenyl-1,3-butadiene
(5c):
Yield 206 mg (79%) as thick gum. IR (neat): ν = 2935, 2220, 1600,
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1
1491, 1040, 928 cm–1. H NMR (200 MHz, CDCl3): δ = 3.83 (s, 3
H, OMe), 5.47 (s, 1 H, C=CHAHB), 5.90 (s, 1 H, C=CHAHB), 6.94 (1Z)-2-Cyano-1-(1-naphthyl)-3-phenyl-1,3-butadiene (5h): Yield
(s, 1 H, ArCH=C), 6.92–6.96 (m, 1 H, Ar), 7.25–7.42 (m, 8 H, Ar)
208 mg (74%). M.p. 81–82 °C. IR (CHCl3 film): ν = 3062, 3019,
˜
ppm. 13C NMR (50 MHz, CDCl3): δ = 55.4, 113.2, 113.5, 117.1,
2223, 1598, 1575, 1509, 1495, 1444, 1051, 1027, 912 cm–1. 1H NMR
117.4, 119.3, 122.2, 128.4, 128.6 (2 C), 128.7 (2 C), 129.8, 134.7, (200 MHz, CDCl3): δ = 5.55 (s, 1 H, C=CHAHB), 5.97 (s, 1 H,
138.3, 144.5, 145.2, 159.8 ppm. EI MS: m/z (%) = 230 (100) [M+
OMe], 216 (22), 203 (27), 190 (16), 178 (16), 153 (56), 115 (32), 101
–
C=CHAHB), 7.46–7.64 (m, 9 H, Ph and Ar), 7.70 (s, 1 H, =CHNp),
7.88 (t, J = 7.4 Hz, 2 H, Ar), 8.05 (d, J = 7.4 Hz, 1 H, Ar) ppm.
(24), 91 (67), 77 (56), 63 (15). GC: (200 °C – 10 °C/min – 260 °C – 13C NMR (50 MHz, CDCl3): δ = 116.5, 117.1, 119.7, 123.2, 125.5,
5 °C/min – 300 °C) tR = 12.46 min (100%). C18H15NO (261.32): 126.3, 126.9, 127.0, 128.5, 128.7 (2 C), 128.8 (2 C), 128.9, 130.7,
calcd. C 82.73, H 5.79, N 5.36; found C 82.34, H 5.83, N 5.20.
130.8, 131.4, 133.4, 138.3, 143.0, 145.0 ppm. ESI MS: m/z (%) =
282 (100) [M+ + H]. HRMS: calcd. for C21H16N (M+ + H)
282.1283, found 282.1276.
(1Z)-2-Cyano-3-(4-methoxyphenyl)-3-phenyl-1,3-butadiene (5d):
Yield 212 mg (81%) as thick gum. IR (neat): ν = 3019, 2935, 2838,
˜
2215, 1602, 1511, 1308, 1260, 1279, 1031, 904, 832, 764 cm–1. H
(1Z)-2-Cyano-1-(2-fuyrl)-3-phenyl-1,3-butadiene (5i): Yield 181 mg
1
NMR (200 MHz, CDCl3): δ = 3.84 (s, 3 H, OMe), 5.41 (s, 1 H,
C=CHAHB), 5.83 (s, 1 H, C=CHAHB), 6.89 (s, 1 H, ArCH=C),
6.90 (d, J = 8.8 Hz, 2 H, Ar), 7.28–7.43 (m, 5 H, Ph), 7.73 (d, J =
(82%) as thick gum. IR (neat): ν = 3140, 3056, 2929, 2218, 1592,
˜
1493, 1469, 1444, 1151, 1088, 1025, 899, 886, 782, 754 cm–1. 1H
NMR (200 MHz, CDCl3): δ = 5.41 (s, 1 H, C=CHAHB), 5.87 (s, 1
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Eur. J. Org. Chem. 2008, 3868–3874