K
S. R. Mangaonkar, F. V. Singh
Paper
Synthesis
GC-MS: m/z (%) = 237 ([M+ + 2], 20), 236 ([M+ + 1], 15), 235 ([M+], 90),
219 (43), 207 (32), 190 (43), 178 (50), 153 (65), 150 (32), 134 (17),
125 (90), 109 (67), 108 (23), 97 (23), 85 (32).
Ethyl 2-Cyano-3-(4-bromophenyl)oxirane-2-carboxylate (3r)
White solid; yield: 235 mg (0.80 mmol, 80%); mp 117–119 C; Rf = 0.4
(hexane).
Anal. Calcd for C12H10FNO3: C, 61.28; H, 4.29; N, 5.95. Found: C, 61.33;
H, 4.32; N, 5.93.
IR (KBr): 681, 693, 734, 771, 842, 854, 889, 1006, 1055, 1161, 1287,
1374, 1476, 1571, 1753, 2216, 2990 cm–1
.
1H NMR (400 MHz, CDCl3): = 1.28 (t, J = 7.2 Hz, 3 H, CH3), 4.28 (td,
J1 = 1.6 Hz, J2 = 6.8 Hz, 2 H, CH2), 4.40 (s, 1 H, CH), 7.21 (d, J = 8.0 Hz, 2
H, ArH), 7.48 (d, J = 8.4 Hz, 2 H, ArH).
Ethyl 2-Cyano-3-(2-chlorophenyl)oxirane-2-carboxylate (3o)
White solid; yield: 166 mg (0.66 mmol (66%); mp 125–127 C; Rf = 0.4
(hexane).
13C NMR (100 MHz, CDCl3): = 13.9, 53.3, 63.8, 64.2, 112.8, 124.8,
IR (KBr): 667, 732, 767, 838, 896, 1010, 1061, 1080, 1110, 1163, 1222,
128.4 (2 C), 129.0, 132.1 (2 C), 162.4,
1270, 1378, 1434, 1446, 1529, 1580, 1760, 2217, 2968 cm–1
.
GC-MS: m/z (%) = 297 ([M+ + 3], 9), 296 ([M+ + 2], 15), 295 ([M+ + 1],
23), 294 ([M+], 100), 268 (28), 250 (43), 222 (40), 212 (53), 184 (80),
158 (17), 143 (50), 89 (90), 85 (54), 63 (43).
1H NMR (400 MHz, CDCl3): = 1.18–1.32 (m, 3 H, CH3), 4.30–4.35 (m,
2 H, CH2), 4.68 (s, 1 H, CH), 7.26–7.36 (m, 4 H, ArH).
13C NMR (100 MHz, CDCl3): = 14.0, 52.7, 62.3, 64.3, 112.6, 127.3 (2
C), 128.7, 129.6, 131.3, 133.6, 162.3.
Anal. Calcd for C12H10BrNO3: C, 48.67; H, 3.40; N, 4.73. Found: C,
48.70; H, 3.43; N, 4.78.
GC-MS: m/z (%) = 253 ([M+ + 2], 16), 252 ([M+ + 1], 24), 251 ([M+],
100), 248 (40), 247 (90), 231 (17), 206 (26), 171 (36), 143 (25), 132
(47), 105 (30), 77 (42), 51 (20).
Ethyl 2-Cyano-3-(4-cyanophenyl)oxirane-2-carboxylate (3s)
White solid; yield: 174 mg (0.72 mmol, 72%); mp 165–167 C; Rf = 0.4
(hexane).
Anal. Calcd for C12H10ClNO3: C, 57.27; H, 4.01; N, 5.57. Found: C,
57.30; H, 4.04; N, 5.60.
IR (KBr): 689, 732, 740, 756, 876, 890, 987, 1012, 1089, 1111, 1140,
1198, 1211, 1257, 1298, 1356, 1390, 1416, 1465, 1589, 1632, 1665,
Ethyl 3-(4-Chlorophenyl)-2-cyanooxirane-2-carboxylate (3p)
1790, 2212, 2789, 3001 cm–1
.
1H NMR (400 MHz, CDCl3): = 1.16–1.34 (m, 3 H, CH3), 4.32–4.52 (m,
White solid; yield: 193 mg (0.77 mmol, 77%); mp 70–72 C; Rf = 0.2
(hexane).
3 H, CH, CH2), 7.48–7.69 (m, 4 H, ArH).
13C NMR (100 MHz, CDCl3): = 13.9, 53.2, 63.2, 64.6, 112.3, 114.3,
117.9, 127.6 (2C), 132.6 (2C), 134.9, 161.9.
GC-MS: m/z (%) = 243 ([M+ + 1], 20), 242 ([M+], 100), 226 (40), 213
(50), 197 (54), 181 (23), 169 (34), 160 (54), 141 (49), 127 (18), 115
(23), 104 (32), 88 (16), 83 (45), 64 (42).
IR (KBr): 681, 734, 771, 841, 890, 1007, 1054, 1073, 1094, 1162, 1201,
1219, 1287, 1374, 1438, 1477, 1491, 1571, 1598, 1753, 2223, 2970
cm–1
.
1H NMR (400 MHz, CDCl3): = 1.28 (t, J = 7.2 Hz, 3 H, CH3), 4.29 (tq,
J1 = 1.2 Hz, J2 = 6.8 Hz, 2 H, CH2), 4.42 (s, 1 H, CH), 7.26–7.36 (m, 4 H,
ArH).
Anal. Calcd for C13H10N2O3: C, 64.46; H, 4.16; N, 11.56. Found: C,
64.50; H, 4.20; N, 11.52.
13C NMR (100 MHz, CDCl3): = 13.9, 53.3, 63.7, 64.3, 112.9, 128.2 (2
C), 128.5, 129.1 (2 C), 136.4, 162.4.
GC-MS: m/z (%) = 253 ([M+ + 2], 27), 252 ([M+ + 1], 18), 251 ([M+], 85),
235 (34), 222 (90), 205 (75), 193 (16), 179 (40), 169 (32), 150 (43),
141 (94), 124 (21), 113 (32), 89 (46), 77 (51), 63 (40).
Ethyl 2-Cyano-3-(3-hydroxyphenyl)oxirane-2-carboxylate (3t)
Colourless solid; yield: 172 mg (0.74 mmol, 74%); mp 122–124 C;
Rf = 0.4 (EtOAc–hexane 1:49).
Anal. Calcd for C12H10ClNO3: C, 57.27; H, 4.01; N, 5.57. Found: C,
57.30; H, 4.06; N, 5.54.
IR (KBr): 680, 687, 740, 760, 779, 920, 1009, 1060, 1110, 1160, 1215,
1284, 1376, 1391, 1440, 1475, 1572, 1599, 1682, 1757, 2231, 2991
cm–1
.
Ethyl 2-Cyano-3-(3-bromophenyl)oxirane-2-carboxylate (3q)
1H NMR (400 MHz, CDCl3): = 1.31 (t, J = 7.2 Hz, 3 H, CH3), 4.32 (tq,
J1 = 2.0 Hz, J2 = 6.8 Hz, 2 H, CH2), 4.39 (s, 1 H, CH), 6.81–6.86 (m, 2 H,
ArH), 6.91 (d, J = 7.6 Hz, 1 H, ArH), 7.21 (t, J = 8.0 Hz, 1 H, ArH).
White solid; yield: 233 mg (0.79 mmol, 79%); mp 155–157 C; Rf = 0.3
(hexane).
13C NMR (100 MHz, CDCl3): = 13.9, 53.2, 64.3, 112.9, 113.4, 117.7,
119.0, 119.1, 130.2, 131.4, 156.3, 162.8.
GC-MS: m/z (%) = 234 ([M+ + 1], 21), 233 ([M+], 60), 232 (70), 204 (28),
186 (60), 151(90), 131(43), 123 (80), 95 (70), 77 (80).
IR (KBr): 681, 693, 733, 772, 787, 854, 918, 1006, 1054, 1112, 1161,
1219, 1285, 1373, 1393, 1438, 1476, 1571, 1598, 1680, 1752, 2219,
2990 cm–1
.
1H NMR (400 MHz, CDCl3): = 1.26 (td, J1 = 0.8 Hz, J2 = 6.0 Hz, 3 H,
CH3), 4.26 (td, J1 = 1.6 Hz, J2 = 8.4 Hz, 2 H, CH2), 4.40 (s, 1 H, CH), 7.18–
7.28 (m, 2 H, ArH), 7.44–7.49 (m, 2 H, ArH).
Anal. Calcd for C12H11NO4: C, 61.80; H, 4.75; N, 6.01. Found: C, 61.83;
H, 4.78; N, 6.03.
13C NMR (100 MHz, CDCl3): = 13.9, 53.3, 63.4, 64.4, 112.7, 122.8,
125.3, 129.9, 130.5, 132.3, 133.5, 162.3.
Ethyl 2-Cyano-3-(4-methylphenyl)oxirane-2-carboxylate (3u)
GC-MS: m/z (%) = 297 ([M+ + 3], 14), 296 ([M+ + 2], 10), 295 ([M+ + 1],
26), 294 ([M+], 100), 268 (29), 249 (52), 222 (41), 212 (59), 184 (92),
163 (18), 142 (30), 89 (91), 84 (48), 65 (20).
Colourless solid; yield: 194 mg (0.84 mmol, 84%); mp 162–164 C;
Rf = 0.4 (hexane).
IR (KBr): 649, 690, 712, 770, 842, 884, 912, 1026, 1141, 1169, 1267,
1323, 1378, 1454, 1590, 1738, 2239, 2790, 2879 cm–1
.
Anal. Calcd for C12H10BrNO3: C, 48.67; H, 3.40; N, 4.73. Found: C,
48.70; H, 3.41; N, 4.75.
1H NMR (400 MHz, CDCl3): = 1.25 (t, J = 7.2 Hz, 3 H, CH3), 2.25 (s, 3
H, CH3), 4.25 (tq, J1 = 1.6 Hz, J2 = 8.0 Hz, 2 H, CH2), 4.38 (s, 1 H, CH),
7.12 (d, J = 8.0 Hz, 2 H, ArH), 7.21 (d, J = 8.4 Hz, 2 H, ArH).
Thieme. All rights reserved. — Synthesis 2019, 51, A–N