X. Hu et al. / Journal of Organometallic Chemistry 705 (2012) 70e74
73
119.4, 120.1, 120.7, 124.2, 124.8, 125.4, 125.8, 128.6, 129.0, 129.2,
134.2, 137.9, 139.4. Anal. Calcd. for C19H16N2: C, 83.79; H, 5.92; N,
10.29. Found: C, 83.66; H, 5.91; N, 10.33.
KCl, FeCl2
H2O
O
H
Ph
CN
O
K4[Fe(CN)6]
Ph
4.3.5. 2-(4-Chlorophenylamino)-2-phenylpropanenitrile (Table 3,
entry 5)
CN
Ph
O
White solid, mp 137e138 ꢁC. IR (KBr): 3379, 2989, 2233, 1601,
OH
1516, 1318, 1257, 807, 699 cmꢀ1 1H NMR (CDCl3, 400 MHz):
d
1.94 (s,
3H), 4.29 (s, 1H), 6.46e6.48 (m, 2H), 7.06e7.08 (m, 2H), 7.26e7.38
(m, 3H), 7.38e7.61 (m, 2H). 13C NMR (CDCl3, 100 MHz):
33.3,
Cl
O
d
57.2, 116.9, 120.4, 124.8, 125.1, 128.8, 129.0, 129.3, 139.4, 142.0. Anal.
Calcd. for C15H13ClN2: C, 70.18; H, 5.10; N, 10.91. Found: C, 70.09; H,
5.11; N, 10.95.
H
C
CN
N
Ph
OH
CN
R1
R2
4.3.6. 2-(Phenylamino)-2-(4-bromophenyl)propanenitrile (Table 3,
entry 6)
R3
O
R1
R2
N
H
R1
R2
White solid, mp 156e157 ꢁC. IR (KBr): 3380, 2936, 2230, 1603,
R3
1514, 1316, 1261, 751, 694 cmꢀ1 1H NMR (CDCl3, 400 MHz):
d
1.91 (s,
3H), 4.27 (s, 1H), 6.50e6.53 (m, 2H), 6.80e6.85 (m, 1H), 7.10e7.26
(m, 2H), 7.49e7.55 (m, 4H). 13C NMR (CDCl3, 100 MHz):
33.3,
R3 NH2
H2O
d
Scheme 3. Proposed mechanism for synthesis of a-aminonitriles from ketones using
56.7, 115.7, 120.2, 122.6, 126.7, 129.1, 132.4, 139.0, 143.1. Anal. Calcd.
for C15H13BrN2: C, 59.82; H, 4.35; N, 9.30. Found: C, 59.88; H, 4.34;
N, 9.35.
K4[Fe(CN)6] as cyanide source.
combined organic layers were dried with anhydrous sodium sulfate
and the solvent was removed by evaporation. The residue was
subjected to column chromatography to give pure product.
4.3.7. 2-(Phenylamino)-2-(4-methoxyphenyl)propanenitrile
(Table 3, entry 7)
White solid, mp 94e95 ꢁC. IR (KBr): 3385, 2932, 2230, 1605,
1514, 1317, 1256, 832, 693 cmꢀ1 1H NMR (CDCl3, 400 MHz):
d 1.93 (s,
4.3. The analytical data for the products
3H), 3.81 (s, 3H), 4.24 (s, 1H), 6.54e6.56 (d, 2H, J ¼ 8.8 Hz),
6.78e6.82 (m, 1H), 6.90e6.92 (m, 2H), 7.10e7.26 (m, 2H), 7.52e7.54
4.3.1. 2-(Phenylamino)-2-phenylpropanenitrile (Table 3, entry 1)
(d, 2H, J ¼ 8.8 Hz). 13C NMR (CDCl3, 100 MHz):
d 33.5, 55.3, 56.6,
White solid, mp135e136 ꢁC. IR (KBr): 3386, 2925, 2228, 1601,
114.5, 115.8, 119.9, 120.8, 126.1, 128.3, 131.7, 143.5, 159.6. Anal. Calcd.
for C16H16N2O: C, 76.16; H, 6.39; N,11.10. Found: C, 76.22; H, 6.40; N,
11.07.
1512,1314,1260, 871, 695 cmꢀ1 1H NMR (CDCl3, 400 MHz):
d 1.95 (s,
3H), 4.28 (s, 1H), 6.53e6.56 (m, 2H), 6.78e6.83 (m, 1H), 7.10e7.14
(m, 2H), 7.26e7.39 (m, 3H), 7.41e7.64 (m, 2H). 13C NMR (CDCl3,
100 MHz):
d
33.4, 57.1, 115.7, 119.9, 120.1, 124.8, 129.0, 129.2, 139.8,
4.3.8. 2-(Phenylamino)-2-(4-nitrophenyl)propanenitrile (Table 3,
entry 8)
143.4. Anal. Calcd. for C15H14N2: C, 81.05; H, 6.35; N,12.60. Found: C,
81.11; H, 6.37; N, 12.55.
White solid, mp 153e154 ꢁC. IR (KBr): 3380, 2937, 2231, 1604,
1519, 1347, 1263, 746, 695 cmꢀ1 1H NMR (CDCl3, 400 MHz):
d 1.97 (s,
4.3.2. 2-(2-Tolylamino)-2-phenylpropanenitrile (Table 3, entry 2)
3H), 4.42 (s, 1H), 6.48e6.50 (d, 2H, J ¼ 8.4 Hz), 6.82e6.86 (m, 1H),
White solid, mp148e149 ꢁC. IR (KBr): 3441, 2987, 2226, 1600,
7.12e7.26 (m, 2H), 7.81e7.85 (d, 2H, J ¼ 7.6 Hz), 8.25e8.29 (d, 2H,
1507, 1311, 1263, 871, 698 cmꢀ1 1H NMR (CDCl3, 400 MHz):
d
1.98 (s,
J ¼ 7.6 Hz). 13C NMR (CDCl3, 100 MHz):
d 33.0, 56.7, 115.6, 119.7,
3H), 2.27 (s, 3H), 4.09 (s, 1H), 6.33e6.35 (d, 1H, J ¼ 8.4 Hz),
120.6, 124.6, 126.1, 129.2, 142.6, 146.9, 148.1. Anal. Calcd. for
C15H13N3O2: C, 67.40; H, 4.90; N, 15.72. Found: C, 67.31; H, 4.91; N,
15.76.
6.71e6.75 (m, 1H), 6.89e6.93 (m, 1H), 7.09e7.11 (m, 1H), 7.33e7.41
(m, 3H), 7.59e7.61 (m, 2H). 13C NMR (CDCl3, 100 MHz):
d 17.7, 33.7,
56.7, 114.2, 119.5, 120.8, 123.4, 124.8, 126.6, 128.5, 129.2, 130.3, 139.8,
141.3. Anal. Calcd. for C16H16N2: C, 81.32; H, 6.82; N, 11.85. Found: C,
81.39; H, 6.82; N, 11.83.
4.3.9. 2-(4-Tolylamino)-2-(4-chlorophenyl)propanenitrile (Table 3,
entry 9)
White solid, mp 156e157 ꢁC. IR (KBr): 3384, 2993, 2230, 1615,
4.3.3. 2-(4-Tolylamino)-2-phenylpropanenitrile (Table 3, entry 3)
White solid, mp 152e153 ꢁC. IR (KBr): 3386, 3024, 2988, 2226,
1618, 1519, 1302, 1258, 807, 696 cmꢀ1 1H NMR (CDCl3, 400 MHz):
1518, 1302, 1257, 807, 511 cmꢀ1 1H NMR (CDCl3, 400 MHz):
d 1.90 (s,
3H), 2.19 (s, 3H), 4.16 (s, 1H), 6.43e6.54 (d, 2H, J ¼ 8.0 Hz),
6.93e6.95 (d, 2H, J ¼ 8.0 Hz), 7.26e7.39 (d, 2H, J ¼ 8.8 Hz),
d
1.94 (s, 3H), 2.19 (s, 3H), 4.16 (s, 1H), 6.45e6.47 (d, 2H,
J ¼ 8.4 Hz), 6.92e6.94 (d, 2H, J ¼ 8.4 Hz), 7.33e7.42 (m, 3H),
7.62e7.64 (m, 2H). 13C NMR (CDCl3, 100 MHz):
20.4, 33.3, 57.4,
7.55e7.58 (d, 2H, J ¼ 8.8 Hz). 13C NMR (CDCl3, 100 MHz):
d 20.4,
33.2, 56.9, 116.1, 120.4, 126.5, 129.4, 129.6, 129.7, 134.4, 138.7, 140.7.
Anal. Calcd. for C16H15ClN2: C, 70.98; H, 5.58; N, 10.35. Found: C,
70.89; H, 5.57; N, 10.33.
d
116.1, 120.8, 124.9, 128.5, 129.2, 129.4, 129.5, 140.0, 141.0. Anal.
Calcd. for C16H16N2: C, 81.32; H, 6.82; N, 11.85. Found: C, 81.24; H,
6.83; N, 11.88.
4.3.10. 1-(Phenylamino)cyclopentanecarbonitrile (Table 3, entry 10)
White solid, mp 67e68 ꢁC. IR (KBr): 3365, 2982, 2942, 2235,
1602, 1520, 1310, 1258, 747, 691 cmꢀ1 1H NMR (CDCl3, 400 MHz):
4.3.4. 2-(1-Naphthylamino)-2-phenylpropanenitrile (Table 3,
entry 4)
d
1.89e1.92 (m, 4H), 2.12e2.17 (m, 2H), 2.36e2.41 (m, 2H), 3.84 (s,
1H), 6.81e6.89 (m, 3H), 7.23e7.27 (m, 2H). 13C NMR (CDCl3,
100 MHz): 23.8, 40.2, 57.4, 115.6, 119.8, 122.2, 129.3, 144.0. Anal.
White solid, mp 138e139 ꢁC. IR (KBr): 3356, 2991, 2229, 1582,
1526,1401, 1236, 767, 698 cmꢀ1 1H NMR (CDCl3, 400 MHz):
d
2.11 (s,
3H), 4.89 (s, 1H), 6.45e6.47 (d, 1H, J ¼ 7.6 Hz), 7.14e7.18 (m, 1H),
7.31e7.96 (m, 10H). 13C NMR (CDCl3, 100 MHz):
33.7, 56.8, 110.4,
d
Calcd. for C12H14N2: C, 77.38; H, 7.58; N, 15.04. Found: C, 77.44; H,
7.56; N, 15.00.
d