Helvetica Chimica Acta – Vol. 92 (2009)
1533
(C¼O), 1586vs (C¼C), 1369w, 1279vs, 1254s, 1147w, 1073w, 1031w, 786w. 1H-NMR (CDCl3): 9.50 (br. s,
NH); 4.45, 4.26 (2q, J ¼ 6.3, 2 MeCH2O); 3.60 – 3.05 (br. m, CHN); 2.10 – 1.10 (m, 5 CH2(cyclohexyl));
1.37, 1.31 (2t, J ¼ 7.2, 2 MeCH2O). 13C-NMR (CDCl3): 168.2, 161.0, 160.4 (3s, C(3), 2 C¼O); 115.5 (s,
CN); 69.6 (s, C(2)); 63.6, 60.7 (2t, MeCH2O); 55.5 (d, CHN); 33.4, 24.6, 23.9 (3t, 5 CH2(cyclohexyl));
14.0, 13.5 (2q, 2 MeCH2O). EI-MS: 295 (19), 294 (91, Mþ), 265 (18), 251 (24), 249 (20), 248 (37), 239
(18), 222 (15), 221 (100), 220 (24), 219 (80), 213 (40), 212 (12), 205 (15), 202 (22), 193 (15), 184 (11), 182
(12), 177 (28), 175 (18), 174 (14), 167 (33), 149 (13), 148 (10), 147 (21), 141 (63), 140 (26), 139 (80), 113
(20), 112 (17), 111 (34), 83 (41), 82 (24), 81 (30). HR-EI-MS: 294.1576 (Mþ, C15H22N2O4þ ; calc.
294.1580). Anal. calc. for C15H22N2O4 (294.35): C 61.21, H 7.53, N 9.52; found: C 61.24, H 7.57, N 9.68.
Diisopropyl (Z)-2-Cyano-3-(cyclohexylamino)but-2-enedioate (12k). Yield 194 mg (60%). PLC
(petroleum ether/CH2Cl2 3 :7). Colorless crystals. M.p. 72 – 748 (MeOH). IR (KBr): 2947m, 2213s (CN),
1745s (C¼O), 1660s (C¼O), 1593vs (C¼C), 1452w (br.), 1351m, 1281vs, 1244m, 1146w, 1099m, 994w,
784w. 1H-NMR (CDCl3): 9.50 (br., NH); 5.32, 5.08 (2 sept., J ¼ 6.3, 2 Me2CHO); 3.00 – 3.50 (br. m,
CHN); 2.20 – 1.10 (br. m, 5 CH2(cyclohexyl)); 1.40, 1.30 (2d, J ¼ 6.3, 2 Me2CHO). 13C-NMR (CDCl3):
167.9, 160.7, 160.6 (3s, C(3), 2 C¼O); 116.6 (s, CN); 69.8 (s, C(2)); 71.9, 68.4, 55.5 (3d, 2 Me2CHO,
CHN); 33.5, 24.6, 24.0 (3t, 5 CH2(cyclohexyl)); 21.6, 21.2 (2q, 2 Me2CHO). EI-MS: 323 (11), 322 (53,
Mþ), 279 (15), 238 (22), 237 (100), 235 (27), 221 (41), 220 (45), 219 (46), 207 (35), 195 (10), 194 (10), 193
(52), 192 (13), 157 (25), 156 (11), 155 (16), 153 (15), 139 (40), 120 (83), 113 (44), 112 (23), 111 (41), 83
(47), 82 (23), 81 (22). HR-EI-MS: 322.1892 (Mþ, C17H26N2O4þ ; calc. 322.1893). Anal. calc. for
C11H14N2O4 (322.41): C 63.33, H 8.13, N 8.69; found: C 63.48, H 8.08, N 8.72.
Dimethyl (Z)-2-Cyano-3-(phenylamino)but-2-enedioate (12l). Yield 254 mg (97%). Colorless
crystals. M.p. 90 – 928 (MeOH). IR (KBr): 3256 m (br.), 2962w, 2215s (CN), 1755vs (C¼O), 1679vs
(C¼O), 1582vs (br., C¼C), 1498w, 1435m, 1273vs (br.), 1155w, 1034m, 779m, 697w. 1H-NMR (CDCl3):
11.00 (br., NH); 7.50 – 7.00, 6.85 – 6.50 (2m, 5 arom. H); 3.85, 3.75 (2s, 2 MeO). 13C-NMR (CDCl3): 168.0,
161.3, 158.7 (3s, C(3), 2 C¼O); 137.0 (s, 1 arom. C); 129.7, 127.5, 122.7 (3d, 5 arom. CH); 115.7 (s, CN);
74.3 (s, C(2)); 53.6, 52.3 (2q, 2 MeO). EI-MS: 261 (10), 260 (68, Mþ), 201 (68), 200 (62), 170 (13), 169
(100), 157 (29), 144 (48), 142 (23), 141 (16), 134 (11), 115 (19), 77 (74). HR-EI-MS: 260.0795 (Mþ,
C13H12N2Oþ4 ; calc. 260.0797). Anal. calc. for C13H12N2O4 (260.25): C 60.00, H 4.65, N 10.76; found: C
60.28, H 4.56, N 11.03.
Diethyl (Z)-2-Cyano-3-(phenylamino)but-2-enedioate (12m). Yield 192 mg (67%). Colorless
crystals. M.p. 76 – 788 (MeOH/dry ice). IR (KBr): 3221m (br.), 2983w, 2213m (CN), 1747s (C¼O),
1
1671s (C¼O), 1599vs (br., C¼C), 1369m, 1278vs (br.), 1229w, 1038m, 780w, 699w. H-NMR (CDCl3):
11.10 (br. s, NH); 7.60 – 6.95 (m, 5 arom. H); 4.38, 4.27 (2q, J ¼ 6.2, 2 MeCH2O); 1.45, 1.15 (2t, J ¼ 6.2,
2 MeCH2O). 13C-NMR (CDCl3): 167.8, 160.9, 159.0 (3s, C(3), 2 C¼O); 137.0 (s, 1 arom. C); 129.6, 127.5,
123.0 (3d, 5 arom. CH); 115.8 (s, CN); 74.5 (s, C(2)); 63.4, 61.5 (2t, 2 MeCH2O); 14.0, 13.3 (2q,
2 MeCH2O). EI-MS: 289 (15), 288 (82, Mþ), 215 (51), 214 (56), 188 (13), 187 (100), 186 (24), 170 (20),
169 (81), 144 (37), 143 (54), 142 (40), 116 (15), 115 (14), 77 (63). HR-EI-MS: 288.1108 (Mþ,
C15H16N2Oþ4 ; calc. 288.1110). Anal. calc. for C15H16N2O4 (288.31): C 62.49, H 5.59, N 9.72; found: C 62.86,
H 5.64, N 9.84.
Diispropyl (Z)-2-Cyano-3-(phenylamino)but-2-enedioate (12n). Yield 143 mg (45%). Colorless
crystals. M.p. 82 – 848 (MeOH). IR (KBr): 2980m, 2209m (CN), 1742vs (C¼O), 1674vs (C¼O), 1560vs
(C¼C), 1583s, 1496w, 1375m, 1353m, 1343w, 1279vs, 1239m, 1182w, 1168w, 1102s, 1006w, 901w, 784w,
1
764w, 699m. H-NMR (CDCl3): 11.05 (br. s, NH); 7.05 – 7.50 (m, 5 arom. H); 5.09, 5.11 (2 sept., J ¼ 6.3,
2 Me2CHO); 1.36, 1.22 (2d, J ¼ 6.3, 2 Me2CHO). 13C-NMR (CDCl3): 167.2, 160.3, 159.2 (3s, C(3),
2 C¼O); 137.0 (s, 1 arom. C); 129.3, 127.3, 123.3 (3d, 5 arom. CH); 115.6 (s, CN); 74.4 (s, C(2)); 71.8, 69.2
(2d, 2 Me2CHO); 21.5, 21.4, 20.8, 20.7 (4q, 2 Me2CHO). EI-MS: 317 (10), 316 (48, Mþ), 274 (28), 232
(30), 215 (15), 214 (13), 188 (26), 187 (100), 186 (18), 170 (47), 169 (37), 168 (14), 174 (14), 160 (33),
144 (32), 143 (46), 142 (23), 116 (11), 115 (12), 77 (45). HR-EI-MS: 316.1423 (Mþ, C17H20N2O4þ ; calc.
316.1423). Anal. calc. for C17H20N2Oþ4 (316.36): C 64.54, H 6.37, N 8.85; found: C 65.18, H 6.46, N 9.07.
Dimethyl (Z)-2-Cyano-3-{[(R)-1-phenylethyl]amino}but-2-enedioate ((R,Z)-12o). Yield 220 mg
(76%). PLC (CHCl3). Colorless, viscous oil. [a]2D0 ¼ ꢀ81.5 (c ¼ 0.2, CH2Cl2). IR (neat): 3227m (br.),
2955m, 2213s (CN), 1749vs (C¼O), 1676vs (C¼O), 1586vs (br., C¼C), 1437m, 1278vs (br.), 1245m,
1
1121m, 1026m, 784m, 765w, 700m. H-NMR (CDCl3): 9.80 (br. s, NH); 7.45 – 7.14 (m, 5 arom. H); 4.71