1908
J. Masllorens et al.
PAPER
1H NMR (250 MHz, CDCl3): = 2.63 (s, 3 H), 5.81 (s, 1 H), 7.37–
7.50 (m, 7 H), 7.96 (BB part of the AA BB system, 2 H, J = 8.75
Hz).
Anal. Calcd for C16H13NO: C, 81.68; H, 5.57; N, 5.95. Found: C,
81.73; H, 5.55; N, 5.76.
(Z)-4-(2 -Cyano-1 -phenylvinyl)acetanilide [(Z)-9c]
After purification by flash chromatography (n-hexane–EtOAc,
70:30), (Z)-9c was obtained.
13C NMR (62.5 MHz, CDCl3): = 26.7, 96.6, 117.3, 128.5, 128.7,
129.4, 130.3, 136.4, 138.2, 143.2, 161.8, 197.2.
MS: m/z (%) = 247 (M+, 43), 232 (100), 203 (21), 177 (18), 88 (15).
Yield: 73%, 88% from non-recovered starting compound 3c; color-
less solid; mp 153–155 °C.
IR (KBr): 3318, 3052, 2212, 1693, 1672, 1598, 1526, 1316 cm–1
Anal. Calcd for C17H13NO: C, 82.57; H, 5.30; N, 5.66. Found: C,
82.66; H, 5.46; N, 5.49.
(E)-3-[4-(Trifluoromethyl)phenyl]-3-phenyl-2-propenenitrile
[(E)-9h]
After purification by flash chromatography (n-hexane–CH2Cl2,
60:40), (E)-9h was obtained together with recovered cinnamonitrile
3e. Yield was calculated by 1H NMR integration. A pure sample of
(E)-9h was isolated by recrystallization from n-pentane.
1H NMR (250 MHz, CDCl3): = 2.21 (s, 3 H), 5.67 (s, 1 H), 7.27–
7.45 (m, 8 H), 7.59 (BB part of the AA BB system, 2 H, J = 8.8
Hz).
13C NMR (62.5 MHz, CDCl3): = 24.3, 93.5, 118.3, 119.3, 128.5,
130.3, 132.1, 138.8, 140.1, 163.1, 169.2.
MS: m/z (%) = 262 (M+, 50), 220 (100), 219 (25), 180 (25), 43 (48).
Yield: 28%, 58% from non-recovered cinnamonitrile; colorless sol-
id; mp 82–84 °C.
IR (KBr): 3052, 2220, 1413, 1325, 1173, 1118, 1067 cm–1.
Anal. Calcd for C17H14N2O: C, 77.84; H, 5.38; N, 10.68. Found: C,
77.63; H, 5.26; N, 10.38.
1H NMR (250 MHz, CDCl3): = 5.78 (s, 1 H), 7.40–7.50 (m, 5 H),
7.43 (AA part of the AA BB system, 2 H, J = 8.5 Hz), 7.65 (BB
part of the AA BB system, 2 H, J = 8.5 Hz). 13C NMR (62.5 MHz,
CDCl3): = 96.8, 117.2, 123.7 (q, J = 270 Hz), 125.6 (q, J = 3.7
Hz), 128.7, 128.8, 129.4, 130.4, 132.0 (q, J = 33 Hz), 136.3, 142.4,
161.5.
(Z)-3-(4-Methylphenyl)-3-phenyl-2-propenenitrile [(Z)-9d]
After purification by flash chromatography (n-hexane–EtOAc,
98:2), (Z)-9d was obtained.
Yield: 75%, 87% with respect to non-recovered starting compound
3d; colorless solid; mp 73–75 °C.
IR (KBr): 3030, 2210, 1592, 1445, 822, 766, 695 cm–1.
1H NMR (250 MHz, CDCl3): = 2.41 (s, 3 H), 5.68 (s, 1 H), 7.23–
7.40 (m, 9 H).
13C NMR (62.5 MHz, CDCl3): = 21.3, 94.2, 118.1, 128.5, 128.6,
129.2, 129.5, 130.3, 134.1, 139.2, 140.3, 163.2.
MS: m/z (%) = 219 (M+, 100), 204 (75), 179 (20), 108 (10).
MS: m/z (%) = 273 (M+, 100), 233 (31), 204 (70), 177 (14).
Anal. Calcd for C16H10F3N: C, 70.33; H, 3.69; N, 5.12. Found: C,
70.02; H, 3.67; N, 5.13.
(Z)-3-(4-Aminophenyl)-3-phenyl-2-propenenitrile [(Z)-9a]
After purification by flash chromatography (n-hexane–EtOAc,
70:30), (Z)-9a was obtained.
Anal. Calcd for C16H13N: C, 87.64; H, 5.97; N, 6.39. Found: C,
87.34; H, 5.62; N, 6.34.
Yield: 60%, 79% with respect to non-recovered starting compound
3a; pale yellow solid; mp 103–105 °C.
(Z)-3-(4-Chlorophenyl)-3-phenyl-2-propenenitrile [(Z)-9f]
After purification by flash chromatography (n-hexane–EtOAc,
95:5), (Z)-9f was obtained.
IR (KBr): 3463, 3360, 3340, 3219, 2205, 1632, 1602, 1516, 1356,
834, 762 cm–1.
1H NMR (250 MHz, CDCl3): = 1.62 (br s, 2 H), 5.48 (s, 1 H), 6.69
(AA part of the AA BB system, 2 H, J = 8.77 Hz), 7.26–7.46 (m,
7 H).
13C NMR (62.5 MHz, CDCl3): = 91.8, 114.3, 118.8, 126.7, 128.4,
128.8, 130.0, 131.4, 139.9, 148.4, 163.1.
MS: m/z (%) = 220 (M+, 100), 219 (33), 205 (11), 180 (31), 165 (7),
Yield: 80%; colorless solid; mp 84–86 °C.
IR (KBr): 3044, 2210, 1571, 1491, 1347, 1087, 830, 759 cm–1.
1H NMR (250 MHz, CDCl3): = 5.74 (s, 1 H), 7.26–7.49 (m, 9 H).
13C NMR (62.5 MHz, CDCl3): = 95.2, 117.5, 128.3, 128.7, 128.8,
130.6, 130.9, 135.4, 136.1, 138.4, 161.8.
96 (13).
MS: m/z (%) = 239 (M+, 72), 204 (100), 203 (37), 177 (23), 88 (34).
Anal. Calcd for C15H12N2: C, 81.79; H, 5.49; N, 12.72. Found: C,
81.57; H, 5.59; N, 12.55.
Anal. Calcd for C15H10ClN: C, 75.16; H, 4.20; N, 5.84. Found: C,
75.41; H, 4.05; N, 5.80.
(Z)-3-(4-Methoxyphenyl)-3-phenyl-2-propenenitrile [(Z)-9b]
After purification by flash chromatography (n-hexane–EtOAc,
90:10), (Z)-9b was obtained.
(Z)-3-[4-(Trifluoromethyl)phenyl]-3-phenyl-2-propenenitrile
[(Z)-9h]
After purification by flash chromatography (n-hexane–CH2Cl2,
80:20), (Z)-9h was obtained.
Yield: 76%; colorless oil; bp 240–245 °C (bulb-to-bulb distillation)/
0.1 mmHg.
Yield: 74%, 86% from non-recovered starting compound 3h; color-
less solid; mp 105–106 °C.
IR (KBr): 3050, 2211, 1325, 1137, 1115, 1068, 850, 765 cm–1.
1H NMR (250 MHz, CDCl3): = 5.85 (s, 1 H), 7.27–7.48 (m, 5 H),
7.55 (AA part of the AA BB system, 2 H, J = 8.05 Hz), 7.73 (BB
part of the AA BB system, 2 H, J = 8.05 Hz).
13C NMR (62.5 MHz, CDCl3): = 96.1, 117.2, 123.6 (q, J = 270
Hz), 125.5 (q, J = 3.5 Hz), 128.2, 128.8, 129.8, 130.7, 131.6 (q,
J = 32.9 Hz), 137.8, 140.5, 161.5.
IR (neat): 3057, 2931, 2839, 2211, 1605, 1512, 1254, 1179, 762
cm–1.
1H NMR (250 MHz, CDCl3): = 3.87 (s, 3 H), 5.60 (s, 1 H), 6.96
(AA part of the AA BB system, 2 H, J = 8.77 Hz), 7.30–7.45 (m,
5 H), 7.41 (BB part of the AA BB system, 2 H, J = 8.77 Hz).
13C NMR (62.5 MHz, CDCl3): = 55.3, 93.4, 113.8, 118.3, 128.5,
128.6, 129.3, 130.2, 131.3, 139.4, 161.0, 162.7.
MS: m/z (%) = 235 (M+, 100), 220 (15), 204 (12), 195 (14), 165
(16).
MS: m/z (%) = 273 (M+, 100), 233 (30), 204 (69), 177 (12).
Synthesis 2002, No. 13, 1903–1911 ISSN 0039-7881 © Thieme Stuttgart · New York