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PAPER
Methyl 3-(4-Methoxyphenylamino)propanoate (6a)
Brown solid; mp 59–60 °C.
Methyl 3-(4-Chlorophenylamino)propanoate (12a)9h
Yellow solid; mp 56–57 °C.
IR (KBr): 3392, 3039, 2996, 2952, 2834, 1734, 1620, 1515, 1462,
1439, 1366, 1238, 1176, 1121, 1092, 1036, 823 cm–1.
1H NMR (CDCl3): d = 2.59–2.62 (t, J = 6.4 Hz, 2 H, CH2), 3.38–
3.41 (t, J = 6.4 Hz, 2 H, CH2), 3.63 (br s, 1 H, NH), 3.69 (s, 3 H,
OCH3), 3.74 (s, 3 H, OCH3), 6.59–6.61 (d, J = 9.2 Hz, 2 H, Ph),
6.77–6.80 (d, J = 9.2 Hz, 2 H, Ph).
1H NMR (CDCl3): d = 2.60–2.63 (t, J = 6 Hz, 2 H, CH2), 3.41–3.44
(t, J = 6.2 Hz, 2 H, CH2), 3.71 (s, 3 H, OCH3), 4.05 (br s, 1 H, NH),
6.53–6.56 (d, J = 8.8 Hz, 2 H, Ph), 7.11–7.14 (d, J = 8.8 Hz, 2 H,
Ph).
13C NMR (CDCl3): d = 33.42, 39.42, 51.71, 114.02, 122.25, 129.03,
146.01, 172.59.
13C NMR (CDCl3): d = 33.65, 40.42, 51.60, 55.65, 114.48, 114.83,
141.65, 152.32, 172.79.
MS (ESI): m/z = 214 [M + H]+.
3-(4-Chlorophenylamino)propanenitrile (13a)
White solid; mp 72–73 °C.
MS (ESI): m/z = 210 [M + H]+.
Anal. Calcd for C11H15NO3: C, 63.14; H, 7.23; N, 6.69. Found: C,
63.01; H, 7.15; N, 6.86.
IR (KBr): 3363, 3050, 2913, 2853, 2255, 1599, 1515, 1493, 1477,
1407, 1316, 1295, 1265, 1216, 1125, 1090, 1061, 824 cm–1.
3-(4-Methoxyphenylamino)propanenitrile (7a)9b,d
Brown solid; mp 58–59 °C.
1H NMR (CDCl3): d = 2.59–2.62 (t, J = 6.4 Hz, 2 H, CH2), 3.44–
3.48 (t, J = 6.4 Hz, 2 H, CH2), 3.29–3.64 (br s, 1 H, NH), 3.77 (s,
3 H, OCH3), 6.60–6.62 (d, J = 9.2 Hz, 2 H, Ph), 6.81–6.83 (d,
J = 8.8 Hz, 2 H, Ph).
13C NMR (CDCl3): d = 18.05, 40.77, 55.68, 114.69, 115.04, 118.31,
140.15, 152.87.
MS (ESI): m/z = 177 [M + H]+.
1H NMR (CDCl3): d = 2.62–2.66 (t, J = 6.6 Hz, 2 H, CH2), 3.48–
3.52 (t, J = 6.4 Hz, 2 H, CH2), 3.99 (br s, 1 H, NH), 6.55–6.57 (d,
J = 8.8 Hz, 2 H, Ph), 7.16–7.18 (d, J = 9.2 Hz, 2 H, Ph).
13C NMR (CDCl3): d = 18.00, 39.78, 114.11, 117.93, 123.22,
129.31, 144.70.
MS (ESI): m/z = 181 [M + H]+.
Anal. Calcd for C9H9ClN2: C, 59.84; H, 5.02; N, 15.51. Found: C,
59.67; H, 4.94; N, 15.68.
Methyl 3-(o-Toluidino)propanoate (14a)
Yellow oil.
Methyl 3-(p-Toluidino)propanoate (8a)9e
Yellow solid; mp 54–56 °C.
IR (KBr): 3428, 3056, 3020, 2924, 1733, 1606, 1587, 1514, 1439,
1369, 1317, 1256, 1194, 1174, 1130, 1052, 748, 665 cm–1.
1H NMR (CDCl3): d = 2.16 (s, 3 H, CH3), 2.68–2.71 (t, J = 6.0 Hz,
2 H, CH2), 3.51–3.54 (t, J = 6.6 Hz, 2 H, CH2), 3.73 (s, 3 H, OCH3),
4.00 (br s, 1 H, NH), 6.65–7.16 (m, 4 H, Ph).
13C NMR (CDCl3): d = 17.32, 33.59, 29.29, 51.64, 109.64, 117.22,
122.40, 127.04, 130.18, 145.45, 172.83.
1H NMR (CDCl3): d = 2.26 (s, 3 H, CH3), 2.61–2.65 (t, J = 6.2 Hz,
2 H, CH2), 3.43–3.46 (t, J = 6.4 Hz, 2 H, CH2), 3.71 (s, 3 H, OCH3),
3.30–4.12 (br s, 1 H, NH), 6.56–6.58 (d, J = 7.6 Hz, 2 H, Ph), 7.00–
7.02 (d, J = 8.0 Hz, 2 H, Ph).
13C NMR (CDCl3): d = 20.28, 33.63, 39.74, 51.61, 113.23, 126.96,
129.72, 145.14, 172.79.
MS (ESI): m/z = 194 [M + H]+.
MS (ESI): m/z = 194 [M + H]+.
3-(p-Toluidino)propanenitrile (9a)9f
White solid; mp 102–103 °C.
Anal. Calcd for C11H15NO2: C, 68.37; H, 7.82; N, 7.25. Found: C,
68.21; H, 7.75; N, 7.43.
1H NMR (CDCl3): d = 2.29 (s, 3 H, CH3), 2.61–2.64 (t, J = 6.4 Hz,
2 H, CH2), 3.49–3.52 (t, J = 6.4 Hz, 2 H, CH2), 3.60 (br s, 1 H, NH),
6.57–6.59 (d, J = 8.4 Hz, 2 H, Ph), 7.05–7.07 (d, J = 8 Hz, 2 H, Ph).
13C NMR (CDCl3): d = 18.02, 20.31, 40.10, 113.28, 118.30, 127.86,
129.96, 143.81.
3-(o-Toluidino)propanenitrile (15a)
Brown oil.
IR (KBr): 3423, 3055, 3019, 2927, 2248, 1605, 1588, 1516, 1475,
1452, 1371, 1314, 1264, 1211, 1135, 1082, 1057, 987, 751 cm–1.
1H NMR (CDCl3): d = 2.20 (s, 3 H, CH3), 2.67–2.70 (t, J = 6.4 Hz,
2 H, CH2), 3.58–3.62 (t, J = 6.4 Hz, 2 H, CH2), 3.89 (br s, 1 H, NH),
6.59–7.28 (m, 4 H, Ph).
13C NMR (CDCl3): d = 17.30, 18.07, 39.59, 109.47, 118.13, 127.74,
127.13, 130.62, 144.02.
MS (ESI): m/z = 161 [M + H]+.
Methyl 3-(Phenylamino)propanoate (10a)5f
Brown solid; mp 37–38 °C.
1H NMR (CDCl3): d = 2.63–2.66 (t, J = 6.4 Hz, 2 H, CH2), 3.46–
3.49 (t, J = 6.4 Hz, 2 H, CH2), 3.72 (s, 3 H, OCH3), 3.98 (br s, 1 H,
NH), 6.64–7.22 (m, 5 H, Ph).
13C NMR (CDCl3): d = 33.62, 39.33, 51.64, 112.97, 117.67, 129.24,
147.46, 172.73.
MS (ESI): m/z = 180 [M + H]+.
MS (ESI): m/z = 161 [M + H]+.
Anal. Calcd for C10H12N2: C, 74.97; H, 7.55; N, 17.48. Found: C,
74.81; H, 7.47; N, 17.65.
Methyl 3-(m-Toluidino)propanoate (16a)
Yellow oil.
3-(Phenylamino)propanenitrile (11a)9g
White solid; mp 47–48 °C.
IR (KBr): 3401, 3027, 2952, 2920, 2859, 1732, 1606, 1514, 1492,
1436, 1366, 1326, 1255, 1171, 1110, 1054, 844, 772, 694 cm–1.
1H NMR (CDCl3): d = 2.30 (s, 3 H, CH3), 2.62–2.65 (t, J = 6.2 Hz,
2 H, CH2), 3.45–3.49 (t, J = 6.4 Hz, 2 H, CH2), 3.71 (s, 3 H, OCH3),
3.10–4.19 (br s, 1 H, NH), 6.45–7.11 (m, 4 H, Ph).
13C NMR (CDCl3): d = 21.51, 33.67, 39.35, 51.63, 110.09, 113.78,
118.61, 129.09, 139.01, 147.49, 172.76.
1H NMR (CDCl3): d = 2.61–2.65 (t, J = 6.4 Hz, 2 H, CH2), 3.50–
3.53 (t, J = 6.4 Hz, 2 H, CH2), 3.93 (br s, 1 H, NH), 6.64–7.27 (m,
5 H, Ph).
13C NMR (CDCl3): d = 18.02, 39.70, 113.02, 118.31, 118.50,
129.41, 146.21.
MS (ESI): m/z = 194 [M + H]+.
MS (ESI): m/z = 147 [M + H]+.
Synthesis 2008, No. 24, 3931–3936 © Thieme Stuttgart · New York