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J. C. Dunham et al.
PAPER
13C NMR (100 MHz, CDCl3): d = 112.8, 38.6, 25.8, 21.2, 20.6.
Anal. Calcd for C11H16N2: C, 74.96; H, 9.15; N, 15.89. Found: C,
75.05; H, 9.17; N, 15.72.
(2,2-Dimethylpropyl)malononitrile (17)12
Malononitrile (0.649 g, 9.82 mmol), trimethylacetaldehyde (3.10 g,
36.0 mmol; 1.73 g, 20.1 mmol),19 and NaBH4 (0.763 g, 20.2 mmol)
yielded an oil (0.889 g, 69%).
(1-Phenylethyl)malononitrile (11)5
Malononitrile (0.672 g, 10.2 mmol), acetophenone (3.63 g, 30.2
mmol), and NaBH4 (0.389 g, 10.3 mmol) yielded an oil (1.11 g,
64%).
IR (thin film, NaCl): 2965, 2918, 2869, 2255, 1477 cm–1.
IR (thin film, NaCl): 3090, 3066, 3033, 2977, 2906, 2255, 1497,
1455, 1387 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.43–7.30 (m, 5 H), 3.85 (d,
J = 6.2 Hz, 1 H), 3.49–3.42 (m, 1 H), 1.65 (d, J = 7.0 Hz, 3 H).
1H NMR (400 MHz, CDCl3): d = 3.74 (t, J = 6.8 Hz, 1 H), 2.01 (d,
J = 7.0 Hz, 2 H), 1.05 (s, 9 H).
13C NMR (100 MHz, CDCl3): d = 113.7, 43.8, 30.8, 28.5, 18.3.
13C NMR (100 MHz, CDCl3): d = 138.1, 129.0, 128.6, 127.1, 112.0,
Benzylmalononitrile (18)4c
Malononitrile (1.28 g, 19.4 mmol), benzaldehyde (6.38 g, 60.1
mmol), and NaBH4 (0.767 g, 20.3 mmol; 0.381 g, 10.1 mmol) yield-
ed a solid (2.51 g, 83%); mp 86–87 °C.
111.8, 40.9, 30.9, 17.6.
Ethylmalononitrile (12)2c
Malononitrile (0.715 g, 10.8 mmol), acetaldehyde (2.37 g, 53.8
mmol), and NaBH4 (0.413 g, 10.9 mmol) yielded an oil (0.847 g,
87%).
IR (thin film, NaCl): 2984, 2917, 2884, 2259, 1462 cm–1.
1H NMR (400 MHz, CDCl3): d = 3.75 (t, J = 6.6 Hz, 1 H), 2.13–
2.06 (m, 2 H), 1.25 (t, J = 7.5 Hz, 3 H).
13C NMR (100 MHz, CDCl3): d = 112.6, 24.6, 23.9, 10.8.
IR (pellet, KBr): 3030, 2915, 2258, 1496, 1454, 1446, 1075, 749,
701 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.43–7.25 (m, 5 H), 3.90 (t,
J = 7.0 Hz, 1 H), 3.28 (d, J = 7.0 Hz, 2 H).
13C NMR (100 MHz, CDCl3): d = 132.9, 129.3, 129.1, 128.8, 112.2,
36.7, 24.9.
(4-Methylbenzyl)malononitrile (19)20
Malononitrile (0.669 g, 10.1 mmol), 4-methylbenzaldehyde (4.18 g,
34.8 mmol), and NaBH4 (0.381 g, 10.1 mmol; 0.188 g, 4.97
mmol)21 yielded a solid (1.05 g, 61%); mp 79–80 °C.
Propylmalononitrile (13)16
Malononitrile (1.33 g, 20.1 mmol), propanal (4.71 g, 81.1 mmol),
and NaBH4 (0.763 g, 20.2 mmol) yielded an oil (1.68 g, 77%).
IR (thin film, NaCl): 2969, 2925, 2879, 2256, 1723 cm–1.
IR (pellet, KBr): 2933, 2258, 1516, 1348, 1030, 790 cm–1.
1H NMR (400 MHz, CDCl3): d = 3.72 (t, J = 7.0 Hz, 1 H), 2.03–
1.98 (m, 2 H), 1.71–1.60 (m, 2 H), 1.03 (t, J = 7.4 Hz, 3 H).
1H NMR (400 MHz, CDCl3): d = 7.05 (s, 4 H), 3.87 (t, J = 7.0 Hz,
1 H), 3.25 (d, J = 7.0 Hz, 2 H), 2.36 (s, 3 H).
13C NMR (100 MHz, CDCl3): d = 112.7, 32.3, 21.2, 19.7, 12.6.
13C NMR (100 MHz, CDCl3): d = 138.6, 129.9, 129.8, 128.9, 112.3,
36.2, 25.0, 21.0.
Butylmalononitrile (14)2c
Malononitrile (2.65 g, 40.1 mmol), butanal (8.62 g, 120 mmol), and
NaBH4 (1.54 g, 40.7 mmol) yielded an oil (3.91 g, 80%).
(4-Methoxybenzyl)malononitrile (20)4c
Malononitrile (0.654 g, 9.90 mmol), 4-methoxybenzaldehyde (3.33
g, 24.5 mmol), and NaBH4 (0.420 g, 11.1 mmol) yielded a solid
(1.04 g, 63%); mp 89–90.5 °C.
IR (thin film, NaCl): 2962, 2933, 2877, 2257, 1468 cm–1.
1H NMR (400 MHz, CDCl3): d = 3.71 (t, J = 7.0 Hz, 1 H), 2.07–
1.99 (m, 2 H), 1.65–1.56 (m, 2 H), 1.47–1.36 (m, 2 H), 0.96 (t,
J = 7.3 Hz, 3 H).
13C NMR (100 MHz, CDCl3): d = 112.8, 35.2, 28.7, 27.2, 22.7,
22.0.
IR (thin film, NaCl): 2934, 2919, 2836, 2257, 1610, 1508, 1249,
1175, 1029 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.24 (d, 2 H, J = 8.8), 6.91 (d,
J = 8.8 Hz, 2 H), 3.85 (t, J = 6.9 Hz, 1 H), 3.81 (s, 3 H), 3.23 (d,
J = 6.9 Hz, 2 H).
(3-Methylbutyl)malononitrile (15)17
Malononitrile (1.37 g, 20.7 mmol), 3-methylbutanal (6.87 g, 79.8
mmol), and NaBH4 (0.787 g, 20.8 mmol) yielded an oil (2.22 g,
78%).
13C NMR (100 MHz, CDCl3): d = 159.8, 130.2, 124.7, 114.5, 112.1,
55.2, 35.9, 25.1.
(4-Nitrobenzyl)malononitrile (21)6
Malononitrile (0.689 g, 10.4 mmol), 4-nitrobenzaldehyde (2.99 g,
19.8 mmol), and NaBH4 (0.202 g, 5.34 mmol; 0.194 g, 5.13
mmol)21 yielded a solid (1.26 g, 60%); mp 151–152.5 °C.
IR (thin film, NaCl): 2960, 2918, 2873, 2256, 1469 cm–1.
1H NMR (400 MHz, CDCl3): d = 3.70 (t, J = 6.8 Hz, 1 H), 2.06–
1.97 (m, 2 H), 1.71–1.59 (m, 1 H), 1.54–1.44 (m, 2 H), 0.94 (d,
J = 5.1 Hz, 6 H).
13C NMR (100 MHz, CDCl3): d = 112.8, 35.2, 28.7, 27.2, 22.7,
22.0.
IR (pellet, KBr): 2930, 2258, 1604, 1520, 1347, 1292, 1106, 858,
790, 712 cm–1.
1H NMR (400 MHz, CDCl3): d = 8.30 (d, J = 8.6 Hz, 2 H), 7.55 (d,
J = 8.6 Hz, 2 H), 4.04 (t, J = 6.5 Hz, 1 H), 3.42 (d, J = 6.5 Hz, 2 H).
(2-Methylpropyl)malononitrile (16)18
Malononitrile (0.680 g, 10.3 mmol), 2-methylpropanal (2.81 g, 39.0
mmol), and NaBH4 (0.419 g, 11.1 mmol) yielded an oil (0.943 g,
75%).
13C NMR (100 MHz, CDCl3): d = 148.3, 139.7, 130.4, 124.5, 111.5,
36.0, 24.4.
Furfurylmalononitrile (22)4c
Malononitrile (1.35 g, 20.4 mmol), furfural (6.02 g, 62.6 mmol),
and NaBH4 (0.812 g, 21.5 mmol; 0.420 g, 11.1 mmol)21 yielded an
oil (2.55 g, 86%).
IR (thin film, NaCl): 2964, 2921, 2876, 2256, 1471, 1392, 1373
cm–1.
1H NMR (400 MHz, CDCl3): d = 3.71 (t, J = 7.5 Hz, 1 H), 1.95–
1.91 (m, 3 H), 1.02 (d, J = 6.2 Hz, 6 H).
IR (thin film, NaCl): 3153, 3126, 2919, 2259, 1599, 1505, 1433,
1147, 1076, 1016, 746 cm–1.
Synthesis 2006, No. 4, 680–686 © Thieme Stuttgart · New York