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Z. Xu et al.
Paper
Synthesis
IR (KBr): 3081, 3024, 2955, 2920, 2848, 2562, 2341, 2218, 1732, 1696,
1606, 1575, 1510, 1445, 1420, 1305, 1259, 1177, 1024, 831, 683, 547
IR (KBr): 3097, 3052, 2368, 2232, 1942, 1689, 1541, 1504, 1402, 1277,
1200, 845, 642 cm–1
.
cm–1
.
1H NMR (400 MHz, CDCl3): δ = 7.80 (s, 4 H).
13C NMR (100 MHz, CDCl3): δ = 132.9, 117.1, 116.9.
1H NMR (400 MHz, CDCl3): δ = 7.62–7.56 (m, 2 H), 6.98–6.93 (m, 2 H),
3.86 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 162.9, 134.1, 119.4, 114.9, 104.1, 55.7.
4-Acetylbenzonitrile (Table 3, Entry 15)
Yield: 639 mg (88%); white solid; mp 53–54 °C.
4-Aminoisophthalonitrile (Table 3, Entry 8)
IR (KBr): 3095, 2923, 2852, 2360, 2228, 1942, 1686, 1603, 1560, 1522,
Yield: 673 mg (94%); yellow solid; mp 215–216 °C.
1473, 1401, 1355, 1293, 1262, 1073, 961, 831, 647, 592 cm–1
.
IR (KBr): 3472, 3374, 3227, 3045, 2348, 2299, 2220, 1639, 1607, 1557,
1429, 1351, 1325, 1282, 1226, 1168, 1144, 911, 829, 790, 732, 690
1H NMR (400 MHz, CDCl3): δ = 8.04 (d, J = 8.4 Hz, 2 H), 7.77 (d, J = 8.4
Hz, 2 H), 2.64 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 196.5, 139.8, 132.4, 128.6, 117.8,
116.3, 26.7.
cm–1
.
1H NMR (400 MHz, CDCl3): δ = 7.89 (d, J = 1.6 Hz, 1 H), 7.39 (dd,
J = 8.4, 2.0 Hz, 1 H), 6.70 (d, J = 8.4 Hz, 1 H), 4.63 (br s, 2 H).
13C NMR (100 MHz, CDCl3): δ = 152.1, 137.1, 136.9, 117.8, 115.4,
101.1, 96.5.
2-Fluorobenzonitrile (Table 3, Entry 16)
Yield: 521 mg (86%); colorless liquid.
IR (KBr): 3360, 2918, 2849, 2235, 1733, 1654, 1635, 1541, 1507, 1472,
2-Amino-3-(trifluoromethyl)benzonitrile (Table 3, Entry 9)
1263, 874, 833, 761 cm–1
.
Yield: 856 mg (92%); white solid; mp 73–75 °C.
1H NMR (400 MHz, CDCl3): δ = 7.61 (m, 2 H), 7.28–7.19 (m, 2 H).
IR (KBr): 3473, 3375, 3349, 3242, 3074, 2921, 2224, 1645, 1572, 1519,
1435, 1359, 1273, 1236, 1143, 1074, 960, 905, 826, 783, 728, 638,
13C NMR (100 MHz, CDCl3): δ = 163.2 (d, J = 258.9 Hz), 135.2 (d, J = 8.3
Hz), 133.6, 124.9 (d, J = 3.8 Hz), 116.6 (d, J = 19.4 Hz), 114.0, 101.6 (d,
J = 15.3 Hz).
595, 544 cm–1
.
1H NMR (400 MHz, CDCl3): δ = 7.63 (m, 1 H), 7.52 (dd, J = 8.8, 1.9 Hz, 1
H), 6.81 (d, J = 8.8 Hz, 1 H), 4.85 (br s, 2 H).
13C NMR (100 MHz, CDCl3): δ = 151.9, 130.8 (q, J = 6.8 Hz), 130.0 (q,
J = 4.1 Hz), 123.5 (q, J = 269.2 Hz), 120.0 (q, J = 33.8 Hz), 116.3, 115.0,
95.2.
Double-Cyanation; General Procedure
To a vial (8 mL) were added Pd(OAc)2 (112 mg, 0.05 mmol), NHC 2
(213 mg, 0.05 mmol), K4[Fe(CN)6]·3H2O (528 mg, 1.25 mmol), Na2CO3
(530 mg, 5 mmol), and an aryl halide (2.5 mmol) under aerobic condi-
tions. The mixture was stirred vigorously at 120 °C. Samples were
taken from the reaction mixture periodically, quenched with H2O, ex-
tracted with EtOAc, and analyzed by GC–MS. After completion of the
reaction, the mixture was allowed to cool to r.t., quenched with H2O
and extracted with EtOAc (3 × 10 mL). The combined extracts were
dried (MgSO4) and the solvent was evaporated. The crude residue was
purified by column chromatography on silica gel (EtOAc–PE).
3-Nitrobenzonitrile (Table 3, Entry 11)
Yield: 492 mg (67%); light yellow solid; mp 109–110 °C.
IR (KBr): 3079, 2924, 2853, 2360, 2236, 1844, 1716, 1540, 1473, 1355,
1288, 1079, 903, 816, 789, 733, 669, 558 cm–1
.
1H NMR (400 MHz, CDCl3): δ = 8.54 (t, J = 1.8 Hz, 1 H), 8.48 (m, 1 H),
8.00 (dt, J = 7.7, 1.3 Hz, 1 H), 7.75 (t, J = 8.0 Hz, 1 H).
13C NMR (100 MHz, CDCl3): δ = 148.2, 137.6, 130.6, 127.5, 127.2,
116.5, 114.1.
1,2-Benzenedicarbonitrile (Table 4, Entry 2)
Yield: 285 mg (89%); white solid; mp 137–140 °C.
IR (KBr): 3079, 3042, 2360, 2232, 2006, 1737, 1661, 1589, 1572, 1484,
4-Nitrobenzonitrile (Table 3, Entry 12)
1447, 1206, 965, 806, 770 cm–1
.
Yield: 533 mg (72%); light yellow solid; mp 108–109 °C.
1H NMR (400 MHz, CDCl3): δ = 7.88–7.81 (m, 2 H), 7.80–7.74 (m, 2 H).
13C NMR (100 MHz, CDCl3): δ = 133.7, 133.3, 116.0, 115.5.
IR (KBr): 3105, 3074, 2924, 2856, 2360, 2232, 1940, 1716, 1697, 1602,
1524, 1488, 1348, 1315, 1294, 1187, 1105, 1015, 859, 747, 682, 539
cm–1
.
2-Fluoro-1,4-benzenedicarbonitrile (Table 4, Entry 5)
1H NMR (400 MHz, CDCl3): δ = 8.39–8.33 (m, 2 H), 7.93–7.86 (m, 2 H).
13C NMR (100 MHz, CDCl3): δ = 150.0, 133.4, 124.2, 118.3, 116.7.
Yield: 292 mg (80%); white solid; mp 122–124 °C.
IR (KBr): 3085, 3053, 2920, 2762, 2684, 2570, 2335, 2047, 1954, 1826,
1781, 1704, 1604, 1550, 1489, 1404, 1268, 1197, 1151, 1120, 980,
1,3-Benzenedicarbonitrile (Table 3, Entry 13)
931, 897, 887, 853, 777, 720, 666, 640, 627 cm–1
.
Yield: 589 mg (92%); white solid; mp 133–134 °C.
1H NMR (400 MHz, CDCl3): δ = 7.92 (d, J = 8.0 Hz, 1 H), 7.68 (dd,
J = 8.0, 1.3 Hz, 1 H), 7.28 (d, J = 1.1 Hz, 1 H).
13C NMR (100 MHz, CDCl3): δ = 166.8 (d, J = 203.8 Hz), 135.7, 129.4,
122.2, 118.7, 116.0, 113.0 (d, J = 17.9 Hz), 110.2 (d, J = 36.5 Hz).
IR (KBr): 3078, 3045, 2920, 2371, 2235, 1749, 1541, 1480, 1423, 1239,
1183, 1148, 906, 872, 806, 679 cm–1
.
1H NMR (400 MHz, CDCl3): δ = 7.96 (m, 1 H), 7.90 (dd, J = 8.0, 1.6 Hz, 2
H), 7.66 (m, 1 H).
13C NMR (100 MHz, CDCl3): δ = 136.1, 135.5, 130.5, 116.7, 114.3.
Biphenyl-4,4′-dicarbonitrile (Table 4, Entry 7)
Yield: 475 mg (93%); white solid; mp 218–221 °C.
1,4-Benzenedicarbonitrile (Table 3, Entry 14)
IR (KBr): 2360, 2226, 1716, 1683, 1603, 1541, 1507, 1489, 1396, 1311,
Yield: 583 mg (91%); white solid; mp 143–144 °C.
1179, 1005, 817, 669, 544 cm–1
.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2015, 47, 1560–1566