5622
A. Mekhalfia et al. / Tetrahedron 62 (2006) 5617–5625
1617, 1495, 1445, 1417, 1398, 1368, 1349, 1310, 1287,
1245, 1223, 1169, 1123, 1099, 1084, 1055, 1029, 994,
entry 3). Pale yellowish powder (123.0 mg, 97%); mp
228–231 ꢁC; IR (neat) nmax 3056, 2965, 2872, 2350, 2340,
2205, 1612, 1578, 1514, 1489, 1450, 1408, 1370, 1328,
1305, 1247, 1220, 1183, 1157, 1111, 1031, 1010, 986,
1
910 cmꢀ1; H NMR (250 MHz, DMSO-d6) d 3.04 (s, 3H,
NCH3), 3.06 (s, 3H, NCH3), 7.28–7.98 (m, 7H, ArH), 8.07
(s, 1H, N]CHN) ppm; 13C NMR (62.5 MHz, DMSO-d6)
d 34.9, 41.2, 101.1, 106.8 (2C), 115.1, 115.5, 127.9, 129.1,
129.9, 130.9, 131.4, 132.5, 133.3, 134.2, 135.1, 158.0,
163.2, 164.6 ppm; ESMS m/z: 424 (M+H)+; HRMS found,
424.0450, C20H15N5SCl requires 424.0457.
1
963 cmꢀ1; H NMR (250 MHz, DMSO-d6) d 1.85 (t, 4H,
J¼7.5 Hz, CH2CH2), 3.50 (t, 4H, J¼7.5 Hz, NCH2), 7.55
(m, 10H, ArH), 8.15 (s, 1H, N]CH) ppm; 13C NMR
(62.5 MHz, CDCl3) d 24.2, 24.8, 46.5, 49.7, 97.7 (2C),
107.4, 115.3, 115.8, 128.3, 128.6 (2C), 128.8 (2C), 128.9,
129.4, 130.5, 133.7, 136.3 (2C), 154.8, 158.8, 163.4,
166.3 ppm; ESMS m/z: 410 (M+H)+; HRMS found,
410.1446, C24H20N5O2S requires 410.1439.
4.2.10. N0-(5-Cyano-pyrimidin-4-yl)-N,N-dimethyl-form-
amidine (Table 2, entry 3). Upon completion the reaction
mixture was concentrated under reduced pressure, before
ice-water (10 mL) was added and the resultant mixture
extracted with EtOAc (2ꢂ10 mL). The organic extract was
dried over anhydrous MgSO4, filtered and the solvent was
evaporated. Drying the solid in vacuo overnight gave the
product as pale yellowish crystals (86.9 mg, 99%); mp
128–132 ꢁC; IR (neat) nmax 3269, 3099, 2869, 2811, 27.05,
2224, 1668, 1585, 1549, 1505, 1412, 1364, 1309, 1236,
4.2.14. 4-Phenyl-2-phenylsulfanyl-6-[(piperidin-1-yl-
methylene)-amino]-pyridine-3,5-dicarbonitrile (Table 3,
entry 4). A mixture of two isomers was obtained as a white
powder (139.0 mg, 90%); mp 196–197 ꢁC; IR (neat) nmax
3060, 2943, 2856, 2211 (s), 1721, 1664 (s), 1603, 1578,
1517, 1485, 1468, 1435, 1407, 1380, 1358, 1295, 1247,
1223, 1202, 1131, 1111, 1078, 1026, 997, 951, 921,
1202, 1136, 1037, 946, 913 cmꢀ1
;
1H NMR (250 MHz,
852 cmꢀ1 1H NMR (250 MHz, CDCl3) major isomer
;
DMSO-d6) d 3.15 (s, 3H, NCH3), 3.30 (s, 3H, NCH3), 8.80
(s, 1H, ArH), 8.85 (s, 1H, ArH), 8.90 (s, 1H, N]CHN) ppm;
13C NMR (62.5 MHz, DMSO-d6) d 34.9, 41.0, 81.0, 100.0,
106.8, 115.6, 157.9, 161.3 ppm; ESMS m/z: 176 (M+H)+;
HRMS found, 176.0937, C8H9N5 requires 176.0936.
d 1.65 (m, 6H, CH2CH2CH2), 3.15 (t, 2H, J¼6.4 Hz,
NCH2), 3.75 (t, 2H, J¼6.4 Hz, NCH2), 7.50–7.60 (m, 10H,
ArH), 8.50 (s, 1H, N]CHN) ppm; (minor isomer) d 1.60
(m, 6H, CH2CH2CH2), 3.27 (t, 2H, J¼6.4 Hz, NCH2),
3.50 (t, 2H, J¼6.4 Hz, NCH2), 7.50–7.60 (m, 10H, ArH),
8.50 (s, 1H, N]CHN) ppm; 13C NMR (62.5 MHz,
CDCl3) d 24.1, 24.7, 25.0, 26.6, 40.6, 44.5, 46.8, 52.0,
97.6 (2C), 115.3, 115.8, 128.0, 128.3, 128.6, 128.8, 128.9,
129.4, 130.5, 133.7, 136.4, 136.4, 156.6, 158.8, 163.7,
166.3 ppm; ESMS m/z: 424 (M+H)+; HRMS found,
424.1581, C25H22N5S requires 424.1596.
4.2.11. 1-Phenyl-5-[(pyrrolidin-1-ylmethylene)-amino]-
1H-pyrazole-4-carbonitrile (Table 2, entry 4). White solid
(104.0 mg, 78% yield); mp 156 ꢁC; IR (neat) nmax 3317,
3104, 3049, 2967, 2872, 2211, 1638, 1609, 1562, 1530,
1502, 1492, 1478, 1455, 1416, 1385, 1325, 1252, 1200, 1174,
1063, 959, 910 cmꢀ1; 1H NMR (250 MHz, CDCl3) d 1.95(m,
4H, NCH2CH2), 3.45 (t, 2H, J¼9.5 Hz, NCH2), 3.55 (t, 2H,
J¼9.5 Hz, NCH2), 7.25–7.90 (m, 6H, ArH), 8.41 (s, 1H,
N]CHN) ppm; 13C NMR (62.5 MHz, CDCl3) d 24.3, 25.1,
45.8, 49.2, 116.2, 123.7, 123.9, 126.9, 128.4, 129.5, 129.9,
141.2, 141.8, 152.5, 154.5 ppm; EIMS m/z: 266 (M+H)+;
HRMS found, 266.1394, C15H17N5 requires 266.1406.
4.2.15. N0-(3,5-Dicyano-4-phenyl-6-phenylsulfanyl-pyri-
din-2-yl)-N-methyl-N-phenyl-formamidine (Table 3,
entry 5). Yellowish solid (91.6 mg, 68%); mp 245–247 ꢁC;
IR (neat) nmax 3051, 2216 (s), 1621, 1606 (s), 1584, 1546,
1515, 1488, 1441, 1419, 1349, 1309, 1283, 1252, 1211,
1117, 1039, 1017, 998, 979, 912, 823, 800, 790, 761 cmꢀ1
;
1H NMR (250 MHz, CDCl3) d 3.50 (s, 3H, NCH3), 7.15–
7.60 (m, 15H, ArH), 8.55 (s, 1H, N]CHN) ppm; 13C
NMR (250 MHz, CDCl3) d 15.2, 35.2, 65.8, 98.8, 98.9,
114.9, 115.5, 121.0, 126.5, 127.7, 128.6, 128.7, 128.9,
129.0, 129.2, 129.3, 129.5, 129.6, 129.9, 130.7, 130.9,
133.4, 135.7, 136.3, 143.4, 156.7, 163.3 ppm; ESMS m/z:
468 (M+Na)+; HRMS found, 468.1240, C27H19N5SNa
requires 468.1259.
4.2.12. N0-(3,5-Dicyano-4-phenyl-6-phenylsulfanyl-pyri-
din-2-yl)-N,N-diethyl formamidine (Table 3, entry 2).
Upon completion the reaction mixture was poured into cold
water (10 mL) and stirred for 5 min. The precipitate formed
was recovered by suction filtration and washed sequentially
with water (10 mL) and petroleum ether (10 mL). Drying
the solid in vacuo gave the product as a white powder
(139.7 mg, 93%); mp 213–215 ꢁC; IR (neat) nmax 3361,
2932, 2748, 2688, 2448, 2270, 2210 (s), 1782, 1720,
1614, 1581, 1537, 1514, 1487, 1451, 1360, 1326, 1255,
4.2.16. N0-(5-Cyano-pyrimidin-4-yl)-N,N-diethyl-form-
amidine (Table 5, entry 1). Upon completion the reaction
mixture was concentrated under reduced pressure, before
ice-water (10 mL) was added and the resultant mixture
extracted with EtOAc (2ꢂ10 mL). The organic extract was
dried over anhydrous MgSO4, filtered and the solvent was
evaporated. Drying the solid in vacuo overnight gave the
product as yellowish crystals (156.0 mg, 77%); mp 152–
154 ꢁC; IR (neat) nmax 3060, 2943, 2211 (s), 1664, 1603
(s), 1517, 1485, 1468, 1380, 1326, 1295, 1247, 1223,
1217, 1171, 1121, 1051, 1035, 1018, 997 cmꢀ1
;
1H
NMR (250 MHz, CDCl3) d 1.12 (2t, 6H, J¼8.0 Hz,
N(CH2CH3)2), 3.25 (q, 2H, J¼8.0 Hz, NCH2CH3); 3.50 (q,
2H, J¼8.0 Hz, NCH2CH3); 7.45–7.65 (m, 10H, ArH), 8.05
(s, 1H, N]CHN) ppm; 13C NMR (62.5 MHz, CDCl3)
d 12.0, 14.4, 38.5, 40.9, 46.7, 75.0, 98.5, 99.0, 112.6,
115.1, 115.4, 125.0, 127.0, 128.5, 128.7, 129.3, 129.9,
130.3, 133.8, 136.0, 157.1, 158.5, 163.1, 165.1 ppm; ESMS
m/z: 412 (M+H)+; HRMS found, 412.1606, C24H22ClN5S
requires 412.1596.
1
1202, 1131, 1111, 1078, 1026, 997, 951 cmꢀ1; H NMR
(250 MHz, CDCl3) d 1.30 (m, 6H, N(CH3)2), 3.45 (q, 2H,
J¼7.5 Hz, NCH2), 3.70 (q, 2H, J¼7.5 Hz, NCH2), 8.55 (s,
1H, ArH), 8.70 (s, 1H, ArH), 8.80 (s, 1H, N]CHN) ppm;
13C NMR (62.5 MHz, CDCl3) d 12.2, 14.4, 41.0, 47.1,
4.2.13. 4-Phenyl-2-phenylsulfanyl-6-[(pyrrolidin-1-yl-
methylene)-amino]-pyridine-3,5-dicarbonitrile (Table 3,