2134
H. Zhang et al.
PAPER
IR (neat): 3356, 2960, 2826, 2245, 1611, 1386, 1090 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.30–7.34 (m, 4 H), 7.23–7.26 (m,
1 H), 3.78–3.38 (m, J = 6.5 Hz, 1 H), 2.6–2.8 (m, 2 H), 2.39–2.43
(m, 2 H), 1.52 (s, 1 H), 1.35–1.36 (d, J = 6.6 Hz, 3 H).
1H NMR (500 MHz, CDCl3): d = 6.79–6.81 (d, J = 7.0 Hz, 2 H),
6.59–6.61 (d, J = 7.0 Hz, 2 H), 3.75 (s, 3 H), 3.45–3.47 (m, J = 6.48
Hz, 2 H), 2.5–2.6 (t, J = 6.48 Hz, 2 H).
ESI-MS: m/z = 175 (M + H)+.
ESI-MS: m/z = 177 (M + H)+.
3-(1-Phenylethylamino)propionic Acid Ethyl Ester (a13)9
From 1-phenylethylamine (1.21 g, 0.01 mol), ethyl acrylate (1.0 g,
0.01 mol), and RuCl3⋅H2O (0.011 g, 0.05 mmol); yield: 1.94 g
(90%); oil.
3-(4-Methoxyphenylamino)propionic Acid Ethyl Ester (b5)21
From 4-methoxyaniline (1.23 g, 0.01 mol), ethyl acrylate (1.0 g,
0.01 mol), and RuCl3⋅H2O (0.011 g, 0.05 mmol); yield: 2.0 g (92%);
yellow solid.
IR (neat): 3356, 2961, 2921, 1738, 1611, 1090 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.27–7.28 (m, 4 H), 7.19–7.20 (m,
1 H), 4.0–4.1 (q, J = 7.0 Hz, 2 H), 3.73–3.74 (q, J = 6.5 Hz, 1 H),
2.65–2.73 (m, 2 H), 2.41–2.43 (m, 2 H), 1.72 (s, 1 H), 1.30–1.31 (d,
J = 6.5 Hz, 3 H), 1.19–1.31 (t, J = 7.1 Hz, 3 H).
IR (neat): 3359, 2926, 2831, 1624, 1513, 1228, 1020 cm–1.
1H NMR (500 MHz, CDCl3): d = 6.8–6.81 (d, J = 7.1 Hz, 2 H),
6.50–6.60 (d, J = 7.1 Hz, 2 H), 4.9 (s, 1 H), 4.2–4.25 (q, J = 7.2 Hz,
2 H), 3.84 (s, 3 H), 3.48–3.51 (q, J = 6.15 Hz, 2 H), 2.60–2.62 (t,
J = 6.15 Hz, 2 H), 1.23–1.27 (t, J = 7.2 Hz, 3 H).
ESI-MS: m/z = 222 (M + H)+.
ESI-MS: m/z = 224 (M + H)+.
2-Methyl-3-(1-phenylethylamino)propionic Acid Methyl Ester
(a14)9
From 1-phenylethylamine (1.21 g, 0.01 mol), methyl methacrylate
(1.02 g, 0.01 mol), and RuCl3⋅H2O (0.011 g, 0.05 mmol); yield: 1.97
g (89%); oil.
3-(4-Methoxyphenylamino)cyclohexanone (b6)
From 4-methoxyaniline (1.23 g, 0.01 mol), cyclohex-2-en-1-one
(0.96 g, 0.01 mol), and RuCl3⋅H2O (0.011 g, 0.05 mmol). The crude
product was purified by flash chromatography on a silica gel col-
umn (eluent: hexanes–EtOAc, 4:1); yield: 1.99 g (91%).
IR (neat): 2950, 2840, 1735, 1603, 1495, 1454, 1196 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.2 (m, 2 H), 7.18 (m, 3 H), 3.6 (s,
3 H), 2.9 (m, 3 H), 2.85 (m, 2 H), 2.63 (m, 2 H), 1.25 (s, 1 H), 1.14
(d, J = 6.6 Hz, 3 H).
IR (neat): 3360, 2924, 2831, 1714, 1613, 1217, 1029 cm–1.
1H NMR (500 MHz, CDCl3): d = 6.8 (d, J = 6.9 Hz, 2 H), 6.6 (d,
J = 7.0 Hz, 2 H), 4.62 (s, 1 H), 3.75 (s, 3 H), 3.65 (m, 1 H), 2.98 (m,
1 H), 2.20–2.56 (m, 5 H), 1.68–1.70 (m, 2 H).
ESI-MS: m/z = 223 (M + H)+.
13C NMR (125 MHz, CDCl3): d = 21.0, 32.84, 43.19, 49.07, 52.30,
56.0, 112.81, 122.65, 135.44, 151.67, 208.24.
3-Phenylaminopropionitrile (b1)20
From aniline (0.93 g, 0.01 mol), acrylonitrile (0.53 g, 0.01 mol), and
RuCl3⋅H2O (0.011 g, 0.05 mmol); yield: 1.4 g (96%); oil.
ESI-MS: m/z = 242 (M + Na)+.
IR (neat): 3356, 2960, 2926, 2245, 1471, 1366, 1080 cm–1.
Anal. Calcd for C13H17NO2: C, 71.21; H, 7.81. Found: C, 71.32; H,
7.75.
1H NMR (500 MHz, CDCl3): d = 7.19–7.24 (m, 2 H), 6.75–6.78 (m,
1 H), 6.6–6.62 (d, J = 7.8 Hz, 2 H), 3.48–3.51 (t, J = 6.5 Hz, 2 H),
2.60–2.62 (t, J = 6.5 Hz, 2 H).
3-(4-Nitrophenylamino)propionitrile (b7)20
From 4-nitroaniline (1.38 g, 0.01 mol), acrylonitrile (0.795 g, 0.015
mol), and RuCl3⋅H2O (0.011 g, 0.05 mmol); yield: 1.73 g (91%);
yellow.
ESI-MS: m/z = 147 (M + H)+.
Phenylaminoacetic Acid Ethyl Ester (b2)20
From aniline (0.93 g, 0.01 mol), ethyl acrylate (1.0 g, 0.01 mol), and
RuCl3⋅H2O (0.011 g, 0.05 mmol); yield: 1.74 g (92%); oil.
IR (neat): 3369, 2968, 2243, 1603, 1601, 1435, 1176, 1091 cm–1.
1H NMR (500 MHz, CDCl3): d = 8.1 (d, J = 9.1 Hz, 2 H), 6.8 (d,
J = 9.1 Hz, 2 H), 3.51–3.53 (t, J = 6.5 Hz, 2 H), 2.56–2.59 (t, J = 6.5
Hz, 2 H).
IR (neat): 3355, 2960, 2916, 1740, 1571, 1386 cm–1.
1H NMR (500 MHz, CDCl3): d = 7.16–7.24 (m, 2 H), 6.69–6.72 (m,
1 H), 6.61–6.62 (d, J = 7.7 Hz, 2 H), 4.02–4.17 (q, J = 7.15 Hz, 2
H), 4.02 (s, 1 H), 3.43–3.45 (t, J = 6.3 Hz, 2 H), 2.59–2.61 (t, J = 6.3
Hz, 2 H), 1.24–1.27 (t, J = 7.15 Hz, 3 H).
ESI-MS: m/z = 192 (M + H)+.
3-(4-Nitrophenylamino)propionic Acid Ethyl Ester (b8)21
From 4-nitroaniline (1.38 g, 0.01 mol), ethyl acrylate (1.0 g, 0.01
mol), and RuCl3⋅H2O (0.011 g, 0.05 mmol); yield: 1.9 g (81%); yel-
low.
ESI-MS: m/z = 194 (M + H)+.
3-Phenylaminocyclohexanone (b3)8
IR (neat): 3392, 2985, 2926, 1723, 1607, 1503 cm–1.
From aniline (0.93 g, 0.01 mol), cyclohex-2-en-1-one (0.96 g, 0.01
mol), and RuCl3⋅H2O (0.011 g, 0.05 mmol). The crude product was
purified by flash chromatography on a silica gel column (eluent:
hexanes–EtOAc, 4:1); yield: 1.64 g (87%).
1H NMR (500 MHz, CDCl3): d = 8.0 (d, J = 9.0 Hz, 2 H), 6.5 (d,
J = 9.0 Hz, 2 H), 4.9 (s, 1 H), 4.15–4.19 (q, J = 7.15 Hz, 2 H), 3.52–
3.56 (q, J = 6.2 Hz, 2 H), 2.62–2.65 (t, J = 6.2 Hz, 2 H), 1.25–1.28
(t, J = 7.15 Hz, 3 H).
IR (neat): 3346, 2896, 1711, 1471, 1386, 1090 cm–1.
ESI-MS: m/z = 239 (M + H)+.
1H NMR (500 MHz, CDCl3): d = 7.29–7.34 (m, 4 H), 7.24 (m, 1 H),
4.6 (s, 1 H), 3.7 (s, 1 H), 2.8 (d, J = 4.2 Hz, 1 H), 2.35–2.47 (m, 3
H), 2.06–2.10 (m, 2 H), 1.77–1.80 (m, 2 H).
3-(4-Nitrophenylamino)cyclohexanone (b9)
From 4-nitroaniline (1.38 g, 0.01 mol), cyclohex-2-en-1-one (0.96
g, 0.01 mol), and RuCl3⋅H2O (0.011 g, 0.05 mmol). The crude prod-
uct was purified by flash chromatography on a silica gel column
(eluent: hexane–EtOAc, 4:1); yield: 1.88 g (87%).
ESI-MS: m/z = 212 (M + Na)+.
3-(4-Methoxyphenylamino)propionitrile (b4)21
From 4-methoxyaniline (1.23 g, 0.01 mol), acrylonitrile (0.53 g,
0.01 mol), and RuCl3⋅H2O (0.011 g, 0.05 mmol); yield: 1.7 g (98%);
yellow solid.
IR (neat): 3378, 2998, 1714, 1601, 1396, 1177, 1092 cm–1.
Synthesis 2005, No. 13, 2129–2136 © Thieme Stuttgart · New York