Spectral Data

IV. Copper(I) Catalyzed Cascade Synthesis of 2-Arylsulfanyl- arylcyanamide

IV.8 Spectral Data

2-(Phenylthio)phenylcyanamide (1a):

White solid, mp 92-94 ^oC; ¹H NMR (CDCl₃, 400 MHz):  7.02 (d, 2H, J = 8.8 Hz), 7.11 (t, 1H, J = 7.6 Hz), 7.17 (d, 1H, J = 7.2 Hz), 7.24 (t, 2H, J = 7.6 Hz), 7.41 (d, 1H, J = 8 Hz), 7.48 (t, 1H, J = 8 Hz), 7.58 (d, 1H, J = 7.6 Hz);

13C NMR (CDCl3, 100 MHz):  110.3, 115.4, 117.5, 124.2, 126.6, 127.1, 129.5, 131.9, 135.1, 137.7, 139.9; IR (KBr): 3135, 2923, 2238, 1590, 1578, 1438, 1410, 1288, 1024, 760, 739, 686, 596 cm^-1; Anal. Calcd. for C₁₃H₁₀N₂S: C, 68.99; H, 4.45; N, 12.37; S, 14.16; found: C, 69.10; H, 4.39; N, 12.32; S, 14.08.

2-(p-Tolylthio)phenylcanamide (1b):

White solid, mp 117-119 ^oC; ¹H NMR (CDCl3, 400 MHz):  2.28 (s, 3H), 6.98 (d, 2H, J = 8 Hz), 7.07 (m, 3H), 7.31 (d, 1H, J = 8 Hz), 7.44 (t, 1H, J = 7.6 Hz), 7.55 (d, 1H, J = 7.6 Hz); ¹³C NMR (CDCl_3, 100 MHz):  21.2, 110.5, 115.5, 118.7, 124.3, 128.0, 130.5, 131.4, 131.6, 137.0, 137.3, 139.7; IR (KBr): 3158, 2961, 2791, 2239, 1588, 1578, 1489, 1449, 1407, 1288, 1165, 1019, 805, 757, 503 cm^-1; Anal.

Calcd. forC14H12N2S: C, 69.97; H, 5.03; N, 11.65; S, 13.34; found: C, 69.89; H, 4.96; N, 11.61;

S, 13.25.

NH CN

S

NH CN

S

Me

2-(4-Aminophenylthio)phenylcyanamide (1c):

White solid, mp 131-133 ^oC; ¹H NMR (CDCl₃, 400 MHz):  3.75 (brs, 2H), 6.59 (d, 2H, J = 8 Hz), 7.03 (m, 3H), 7.26 (d, 1H, J = 8 Hz), 7.36 (t, 1H, J = 7.6 Hz), 7.47 (d, 1H, J = 8 Hz); ¹³C NMR (CDCl3, 100 MHz):  110.6, 115.3, 116.3, 121.2, 121.5, 124.2, 130.7, 131.8, 135.9, 138.6, 146.6; IR (KBr): 3394, 3310, 3100, 2802, 2227, 1590, 1579, 1490, 1449, 1412, 1287, 1258, 1138, 817, 764, 609 cm^-1; Anal. Calcd.

for C₁₃H₁₁N₃S: C, 64.70; H, 4.59; N, 17.41; S, 13.28; found: C, 64.63; H, 4.61; N, 17.32; S, 13.21.

2-(4-Nitrophenylthio)phenylcyanamide (1d):

Gummy; ¹H NMR (CDCl3, 400 MHz):  7.06 (d, 2H, J = 9.2 Hz), 7.23 (d, 1H, J = 9.2 Hz), 7.36 (d, 1H, J = 9.2), 7.46 (m, 2H), 7.61 (d, 1H, J = 9.2 Hz), 8.07 (d, 1H, J = 9.2 Hz), 8.11 (d, 1H, J = 9.2); ¹³C NMR (CDCl3, 100 MHz):

 116.0, 121.7, 124.5, 124.7, 125.7, 126.0, 129.8, 131.8, 131.3, 135.9, 146.7, 151.1; IR (KBr):

3292, 3099, 2925, 2853, 2235, 1580, 1509, 1493, 1338, 1305, 1283, 1183, 1110, 912, 815, 741 cm^-1; Anal. Calcd. forC13H9N3O2S: C, 57.55; H, 3.34; N, 15.48; S, 11.82; found: C, 57.49; H, 3.29; N, 15.38; S, 11.69.

N-(4-Nitrophenyl)benzo[d]thiazole-2-amine(1d’):

Yellow solid, mp 211-213 ^oC; ¹H NMR (CDCl₃, 400 MHz): δ 6.62 (d, 1H, J = 9.28 Hz), 7.10 (m, 2H), 7.32 (d, 1H, J = 8.8 Hz), 7.67 (d, 2H, J = 9.2 Hz), 7.42 (d, 2H, J = 8.4 Hz); ¹³C NMR (CDCl₃, 100 MHz): δ 110.5, 122.2, 123.1, 123.3, 125.6, 126.6, 129.8, 140.5, 142.1, 147.5, 162.3; IR (KBr): 3327, 3076, 2929, 2856, 1610, 1580, 1520, 1495, 1470, 1346, 1215, 1108, 1077, 910, 852, 805, 745 cm^-1; Anal. Calcd. for C₁₃H₉N₃O₂S: C, 57.55; H, 3.34; N, 15.49; S, 11.81; found: C, 57.43; H, 3.29; N, 15.43; S, 11.74.

2-(2-Nitrophenylthio)phenylcyanamide (1e):

Yellow solid, mp 155-157 ^oC; ¹H NMR (CDCl3, 400 MHz): δ 6.64 (d, 1H, J = 8 Hz),7.09 (brs, 1H), 7.23 (t, 1H, J = 8.8 Hz),7.31 (t, 1H, J = 8.4 Hz), 7.42 (m, 2H), 7.61 (m, 2H), 8.28 (d, 1H, J = 8 Hz); ¹³C NMR (CDCl3, 100 MHz): δ 110.1, 116.0, 121.7, 124.5, 124.7, 125.7, 126.0, 129.8, 131.3, 135.9,

S NH CN

NH2

S NH CN

NO2

S

N H

N NO₂

S NH CN

NO₂

138.5,142.6,146.7; IR (KBr): 3197, 2901, 2829, 2236, 1592, 1567, 1517, 1490, 1449, 1441, 1337, 1305, 1290, 1163, 1107, 1041, 910, 854, 757 cm^-1; Anal. Calcd. forC13H9N3O2S: C, 57.55;

H, 3.34; N, 15.49; S, 11.81; found: C, 57.39; H, 3.25; N, 15.38; S, 11.77.

N-(2-Nitrophenyl)benzo[d]thiazole-2-amine (1e’):

Yellow solid, mp 155-157 ^oC; ¹H NMR (CDCl₃, 400 MHz): δ 6.64 (d, 1H, J = 8 Hz),7.09 (brs, 1H), 7.23 (t, 1H, J = 8.8 Hz),7.31 (t, 1H, J = 8.4 Hz), 7.42 (m, 2H), 7.61 (m, 2H), 8.28 (d, 1H, J = 8 Hz); ¹³C NMR (CDCl3, 100 MHz): δ 110.1, 116.0, 121.7, 124.5, 124.7, 125.7, 126.0, 129.8, 131.3, 135.9, 138.5,142.6,146.7; IR (KBr): 3197, 2901, 2829, 2236, 1592, 1567, 1517, 1490, 1449, 1441, 1337, 1305, 1290, 1163, 1107, 1041, 910, 854, 757 cm^-1; Anal. Calcd. forC13H9N3O2S: C, 57.55;

H, 3.34; N, 15.49; S, 11.81; found: C, 57.39; H, 3.25; N, 15.38; S, 11.77.

Benzo[d]thiazol-2-amine (K):

White solid, mp 120-122 ^oC; ¹H NMR (CDCl₃, 400 MHz):  5.2 (brs, 2H), 7.13 (t, 1H, J = 8 Hz), 7.31 (t, 1H, J = 8 Hz), 7.53 (d, 1H, J = 8 Hz), 7.58 (d, 1H, J = 8 Hz); ¹³C NMR (CDCl₃, 100 MHz):  119.3, 121.4, 122.7, 126.5, 131.6, 152.1, 167.1; IR (KBr): 3388, 3175, 2925, 2851, 1644, 1528, 1446, 1374, 1284, 1236, 1106, 887, 741 cm^-1; Anal. Calcd. forC7H6N2S: C, 55.97; H, 4.02; N, 18.65; S, 21.34; found: C, 55.84; H, 4.07; N, 18.57; S 21.29.

4-Methyl-2-(phenylthio)phenylcyanamide (2a):

Yellow solid, mp 131-133 ^oC; ¹H NMR (CDCl3, 400 MHz):  2.32 (s, 2H), 6.08 (brs, 1H), 7.02 (d, 2H, J = 7.2 Hz), 7.18 (d, 2H, J = 7.2 Hz), 7.25 (m, 3H), 7.40 (s, 1H); ¹³C NMR (CDCl3, 100 MHz):  20.7, 110.7, 115.4, 117.2, 129.6, 132.7, 134.1, 135.4, 137.5, 138.0; IR (KBr): 3212, 2920, 2840, 2224, 1606, 1580, 1495, 1439, 1387, 1286, 1154, 1072, 1024, 806, 746 cm^-1; Anal. Calcd. for C14H12N2S: C, 69.97;

H, 5.03; N, 11.65; S, 13.34; found: C, 69.83; H, 5.07; N, 11.52; S, 13.21.

S

N H

N O₂N

S N

NH₂

S NH CN

Me

2-(p-Tolylthio)-4-methylphenylcyanamide (2b):

White solid, mp 105-107 ^oC; ¹H NMR (CDCl₃, 400 MHz):  2.29 (s, 3H), 2.31 (s, 3H), 6.96 (d, 2H, J = 8 Hz), 7.06 (d, 2H, J = 8 Hz), 7.22 (m, 2H), 7.37 (s, 1H); ¹³C NMR (CDCl3, 100 MHz):  20.7, 21.1, 110.6, 115.3, 118.0, 127.7, 130.4, 131.5, 132.3, 134.1, 136.9, 137.1, 137.6; IR (KBr): 3153, 2922, 2846, 2231, 1607, 1498, 1410, 1389, 1288, 1155, 1080, 1015, 809, 591 cm^-1; Anal. Calcd. for C₁₅H₁₄N₂S: C, 70.83; H, 5.54; N, 11.01; S, 12.60; found: C, 70.71; H, 5.47; N, 11.08; S, 12.47.

2-(4-Aminophenylthio)-4-methylphenylcyanamide (2c):

White solid, mp 110-112 ^oC; ¹H NMR (CDCl3, 400 MHz):  2.27 (s, 3H), 6.58 (d, 2H, J = 8 Hz), 6.90 (d, 2H, J = 8 Hz), 7.01 (d, 1H, J = 7.6 Hz), 7.15 (s, 1H), 7.28 (d, 1H, J = 7.6 Hz); ¹³C NMR (CDCl3, 100 MHz):  20.7,115.3, 116.2, 116.3, 120.9, 121.8, 130.8, 131.3, 131.6, 133.9, 136.2, 146.5; IR (KBr): 3381, 2923, 2222, 1627, 1495, 1459, 1388, 1288, 1177, 816, 731 cm^-1; Anal. Calcd. for C14H13N3S: C, 65.85; H, 5.13; N, 16.45; S, 12.55; found: C, 65.71; H, 5.16; N, 16.51; S, 12.42.

2-(4-Nitrophenylthio)-4-methylphenylcyanamide (2d):

Gummy; ¹H NMR (CDCl₃, 400 MHz):  2.36 (s, 3H), 7.05 (d, 2H, J = 9.2 Hz),7.31(d, 1H, J = 8.4 Hz),7.39 (d, 2H, J = 8 Hz), 8.09 (d, 2H, J = 9.2 Hz); ¹³C NMR (CDCl3, 100 MHz):  20.7, 112.2, 116.2, 124.6, 125.7, 126.0, 133.9, 134.5, 138.2, 138.7, 145.5; IR (KBr): 3326, 2927, 2851, 2243, 1604, 1505, 1339, 1237, 1110, 1014, 985, 849, 808, 742 cm^-1; Anal. Calcd. for C₁₄H₁₁N₃O₂S: C, 58.93; H, 3.88; N, 14.72; S, 11.23; found: C, 58.99; H, 3.76; N, 14.64; S, 11.17.

6-Methyl-N-(4-nitrophenyl)benzo[d]thiazol-2-amine (2d’):

Gummy, ¹H NMR (CDCl3, 400 MHz):  2.3 (s, 3H), 6.52 (d, 1H, J = 8 Hz), 6.93 (d, 1H, J = 8.4 Hz), 7.14 (s, 1H), 7.66 (d, 2H, J = 8.8 Hz), 8.41 (d, 2H, J = 8.8 Hz); ¹³C NMR (CDCl3, 100 MHz):  21.1, 110.3, 122.5, 123.0, 125.3, 125.6, 127.3, 129.7, 133.3, 128.3, 142.2, 162.6;

IR (KBr): 3336, 3053, 2919, 2850, 1610, 1523, 1497, 1345, 1245, 1109, 848, 805, 738 cm^-1;

S NH CN

Me

Me

S NH CN

Me

NH2

S NH CN

NO₂ Me

S

N H

N NO₂

Me

Anal. Calcd. forC₁₄H₁₁N₃O₂S: C, 58.93; H, 3.88; N, 14.72; S, 11.23; found: C, 58.85; H, 3.79;

N, 14.76; S, 11.11.

2-(2-Nitrophenylthio)-4-methylphenylcyanamide(2e):

Gummy; NMR (CDCl3, 400 MHz):  2.36 (s, 3H), 6.66 (d, 1H, J = 9.2 Hz), 7.28 (m, 2H), 7.40 (m, 3H), 8.25 (d, 1H, J = 9.2 Hz); ¹³C NMR (CDCl3, 100 MHz):  20.7, 110.5, 115.4, 116.0, 126.1, 126.5, 127.3, 133.9, 134.5, 134.8, 136.1, 138.3, 138.6, 145.4; IR (KBr): 3216, 2927, 2853, 2243, 1717, 1511, 1155, 1106, 1041, 955, 911, 853, 816, 783 cm^-1; Anal. Calcd. for C14H11N3O2S: C, 58.93; H, 3.88; N, 14.72; S, 11.23; found: C, 58.85; H, 3.92; N, 14.75; S, 11.12.

6-Methyl-N-(2-nitrophenyl)benzo[d]thiazol-2-amine (2e’):

Gummy; ¹H NMR (CDCl₃, 400 MHz):  2.32 (s, 3H), 6.00 (brs, 2H), 637 (d, 1H, J = 8.4 Hz), 6.91 (d, 1H, J = 8.0 Hz), 7.14 (d, 1H, J = 3.2 Hz), 7.56 (d, 1H, J = 8.0 Hz), 7.65 (t, 1H, J = 8.0), 7.82 (t, 1H, J = 8.0 Hz), 8.19 (d, 1H, J = 9.6 Hz); ¹³CNMR (CDCl₃, 100 MHz):  21.2, 110.1, 122.6, 123.1, 126.6, 127.4, 129.6, 130.7, 132.0, 133.3, 135.2, 138.2, 147.0, 163.4; IR (KBr): 3332, 3094, 2925, 1717, 1613, 1531, 1493, 1361, 1236, 1096, 984, 849, 783 cm^-1; Anal. Calcd. for C₁₄H₁₁N₃O₂S (285.32): C, 58.93; H, 3.88; N, 14.72; S, 11.23; found: C, 58.86; H, 3.93; N, 14.69; S, 11.09.

4-Methoxy-2-(phenylthio)phenylcyanamide (3a):

White solid, mp 119-121 ^oC; ¹H NMR (CDCl3, 400 MHz):  3.78 (s, 3H), 7.01 (d, 1H, J = 2.8 Hz), 7.05 (d, 2H, J = 7.2 Hz), 7.10 (d, 1H, J = 2.8 Hz), 7.18 (t, 1H, J = 7.6 Hz), 7.25 (m, 3H); ¹³C NMR (CDCl₃, 100 MHz):  56.0, 111.0, 116.6, 117.8, 118.6, 122.0, 126.9, 127.3, 129.7, 133.0, 134.9, 156.1; IR (KBr): 3189, 2999, 2962, 2926, 2851, 2228, 1605, 1578, 1497, 1438, 1393, 1257, 1215, 1176, 1043, 1031, 884, 831, 751 cm^-1; Anal. Calcd. for C14H12N2OS: C, 65.60; H, 4.71; N, 10.92; S, 12.50; found: C, 65.53; H, 4.67; N, 10.98; S, 12.49.

S NH CN

NO₂ Me

S

N H

N O₂N H₃C

S NH CN

MeO

2-(4-Aminophenylthio)-4-methoxyphenylcyanamide (3c):

Gummy; ¹H NMR (CDCl₃, 400 MHz):  3.77 (s, 3H), 6.46 (d, 2H, J

= 8.8 Hz), 6.90 (dd, 1H, J = 6.0 Hz, J = 2.8 Hz), 7.06 (d, 1H, J = 6.8 Hz), 7.20 (d, 1H, J = 7.2 Hz) 7.39 (d, 2H, J = 8.8 Hz); ¹³C NMR (CDCl3, 100 MHz):  56.1, 110.5, 111.0, 115.1, 117.2, 117.6, 118.4, 128.7, 138.1, 146.3, 156.4;

IR (KBr): 3381, 2926, 2852, 2236, 1621, 1487, 1375, 1265, 1218, 1179, 1034, 816, 737 cm^-1; Anal. Calcd. for C₁₄H₁₃N₃OS: C, 61.97; H, 4.82; N, 15.48; S, 11.81; found: C, 61.86; H, 4.75; N, 15.56; S, 11.72.

2-(2-Nitrophenylthio)-4-methoxyphenylcyanamide (3e):

Gummy; ¹H NMR (CDCl3, 400 MHz):  3.8 (s, 3H), 6.8 (d, 1H, J = 8 Hz), 7.14 (d, 1H, J = 8.8 Hz), 7.30 (m, 3H), 7.42 (t, 1H, J = 8.8 Hz), 8.28 (d, 1H, J = 8 Hz); ¹³C NMR (CDCl₃, 100 MHz):  56.1, 116.5, 117.2, 119.3, 122.5, 125.7, 126.3, 126.6, 127.2, 128.8, 134.0, 134.6, 145.4, 156.5; IR (KBr): 3217, 2925, 2853, 2241, 1591, 1567, 1505, 1395, 1337, 1293, 1216, 1148, 1041, 853, 783, 734 cm^-1; Anal. Calcd. for C14H11N3O3S: C, 55.80; H, 3.67; N, 13.94; S, 10.64; found: C, 55.69; H, 3.73; N, 13.88; S, 10.58.

6-Methoxy-N-(2-nitrophenyl)benzo[d]thiazol-2-amine (3e’):

Gummy; ¹H NMR (CDCl₃, 400 MHz):  3.78 (s, 3H), 6.40 (d, 1H, J

= 8.8 Hz), 6.66 (dd, 1H, J = 6.0 Hz, J = 2.8 Hz), 6.9 (d, 1H, J = 2.8 Hz), 7.57 (d, 1H, J = 8 Hz), 7.66 (t, 1H, J = 8.8 Hz), 7.82 (t, 1H, J = 7.6 Hz), 8.19 (d, 1H, J = 8 Hz); ¹³C NMR (CDCl3, 100 MHz):  56.1, 108.1, 110.6, 112.7, 124.2, 126.6, 129.9, 130.4, 131.9, 134.4, 135.1, 147.1, 156.2, 162.6; IR (KBr): 3333, 2936, 2835, 1614, 1584, 1531, 1488, 1351, 1269, 1210, 1059, 1031, 849, 784 cm^-1; anal. calcd. for C14H11N3O3S: C, 55.80; H, 3.67; N, 13.94; S, 10.64; found: C, 55.71; H, 3.63; N, 13.89; S, 10.57.

S NH CN

MeO

NH2

S NH CN

NO₂ MeO

S

N H

N H₃CO

O₂N

4-Bromo-2-(phenylthio)phenylcyanamide (4a):

White solid, mp 104-106 ^oC; ¹H NMR (CDCl₃, 400 MHz):  7.07 (d, 2H, J

= 8 Hz), 7.26 (m, 4H), 7.57 (dd, 1H, J = 6 Hz, J = 2.4 Hz), 7.70 (d, 1H, J = 2.4 Hz); ¹³C NMR (CDCl3, 100 MHz):  109.7, 116.2, 116.9, 127.4, 127.8, 129.9, 134.0, 134.7, 138.9, 139.5; IR (KBr): 3201, 3049, 2925, 2846, 2224, 1569, 1479, 1440, 1375, 1280, 1153, 1086, 1023, 888, 805, 741, 691 cm^-1; Anal. Calcd. for C₁₃H₉BrN₂S: C, 51.16;

H, 2.97; N, 9.17; S, 10.50; found: C, 51.08; H, 2.92; N, 9.23; S, 10.43.

2-(p-Tolylthio)-4-bromophenylcyanamide (4b):

White solid, mp 114-116 ^oC; IR (KBr): ν = 3148, 2920, 2234, 1670, 1569, 1481, 1447, 1406, 1378, 1283, 1155, 1084, 816, 804 cm^-1; ¹H NMR (CDCl3, 400 MHz):  = 2.2 (s, 3H), 6.93 (d, 2H, J = 8.4 Hz), 7.00 (d, 2H, J = 8 Hz), 7.08 (d, 2H, J = 8.8 Hz), 7.42 (dd, 1H, J = 6.4 Hz, J = 2.4 Hz), 7.55 (d, 1H, J = 2.4 Hz); ¹³C NMR (CDCl3, 100 MHz):  = 21.3, 110.1, 116.1, 117.0, 128.8, 130.2, 130.7, 131.0, 134.2, 137.8, 138.6, 138.8; Anal. Calcd. for C14H11BrN2S: C, 52.67; H, 3.47; N, 8.77; S, 10.04;

found: C, 52.55; H, 3.41; N, 8.69; S, 9.91.

2-(4-Aminophenylthio)-4-bromophenylcyanamide (4c):

White solid, mp 128-130 ^oC; ¹H NMR (CDCl₃, 400 MHz):  3.82 (brs, 2H), 6.6 (d, 2H, J = 8.4 Hz), 7.08 (d, 2H, J = 8.4 Hz), 7.30 (d, 1H, J = 8.4 Hz), 7.43 (dd, 1H, J = 6.4, J = 2.4), 7.51 (d, 1H, J = 2.0 Hz); ¹³C NMR (CDCl3, 100 MHz):  110.1, 116.2, 116.4, 116.8, 119.9, 124.2, 132.9, 133.0, 137.1, 137.3, 147.2; IR (KBr): 3400, 3332, 3078, 2917, 2239, 1592, 1570, 1480, 1411, 1376, 1262, 1227, 1178, 1086, 848, 769 cm^-1; Anal. Calcd. for C₁₃H₁₀BrN₃S: C, 48.76; H, 3.14; N, 13.12; S, 10.01;

found: C, 48.68; H, 3.18; N, 13.16; S, 9.92.

4-(2-Methyl-1,3-dithiolane-2-yl)-2-(phenylthio)phenylcyanamide (5a):

Oily liquid ¹H NMR (CDCl3, 400 MHz):  2.12 (s, 3H), 3.36 (m, 2H), 4.45 (m, 2H), 7.02 (d, 2H, J = 8 Hz), 7.16 (t, 1H, J = 7.6 Hz), 7.25 (m, 2H), 7.85 (dd, 1H, J = 6.4 Hz, J = 2.4 Hz), 7.97 (d, 1H, J = 2.0 Hz); ¹³C

S NH CN

Br

S NH CN

Br

Me

S NH CN

Br

NH₂

S NH CN

H₃C

S S

NMR (CDCl₃, 100 MHz):  33.7, 40.9, 67.7, 115.1, 116.9, 126.8, 127.1, 129.7, 130.8, 135.1, 136.2, 138.8, 142.5; IR (neat): 3211, 2923, 2851, 2244, 1681, 1596, 1494, 1440, 1385, 1291, 1159, 1078, 824, 739 cm^-1; Anal. Calcd. for C₁₇H₁₆N₂S₃: C, 59.26; H, 4.68; N, 8.13; S, 27.92;

found: C, 59.18; H, 4.61; N, 8.09; S, 27.81.

2-(p-Tolylthio)-4-(2-methyl-1,3-dithiolan-2-yl)-phenylcyanamide (5b):

Oily liquid; ¹H NMR (CDCl3, 400 MHz):  2.12 (s, 3H), 2.28 (s, 3H), 3.36 (m, 2H), 3.46 (m, 2H), 6.96 (d, 2H, J = 8.4 Hz), 7.06 (d, 2H, J = 8 Hz), 7. 24 (d, 1H, J = 8.8 Hz), 7.83 ( dd, 1H, J = 6.0 Hz, J = 2.4 Hz), 7.96 (d, 1H, J = 2.0 Hz); ¹³C NMR (CDCl3, 100 MHz):  21.2, 33.7, 40.8, 67.7, 110.4, 115.0, 117.8, 127.7, 130.5, 131.2, 135.8, 137.0, 138.5, 142.4; IR (neat):

3217, 2976, 2863, 2245, 1597, 1574, 1494, 1385, 1292, 1275, 1084, 1016, 908, 804 cm^-1; Anal.

Calcd. for C18H18N2S3: C, 60.29; H, 5.05; N, 7.81; S, 26.82; found C, 60.21; H, 5.09; N, 7.88; S, 26.76.

2-(4-Aminophenylthio)-4-(2-methyl-1,3-dithiolan-2-yl)-phenylcyanamide (5c):

Oily liquid; ¹H NMR (CDCl₃, 400 MHz):  = 2.09 (s, 3H), 3.33 (m, 2H), 3.45 (m, 2H), 3.75 (brs, 2H), 6.59 (d, 2H, J = 8.8 Hz), 7.01 (d, 2H, J = 8.4 Hz), 7.18 (d, 1H, J = 8.4 Hz), 7.75 (dd, 1H, J = 6.4 Hz, J

= 2.4 Hz), 7.88 (d, 1H, J = 2.4 Hz); ¹³C NMR (CDCl3, 100 MHz):  = 33.6, 40.8, 68.7, 110.6, 114.9, 116.3, 120.3, 121.4, 129.6, 131.5, 134.5, 137.6, 142.1, 146.5; IR (neat): 3367, 2975, 2923, 2225, 1620, 1596, 1495, 1384, 1290, 1178, 1077, 908, 823, 733 cm^-1; Anal. Calcd. for C17H17N3S3: C, 56.79; H, 4.76; N, 11.68; S, 26.75; found: C, 56.71; H, 4.72; N, 11.76; S, 26.63.

6-(2-Methyl-1,3-dithiolan-2-yl)-benzo[d]thiazol-2-amine (5f):

Oily liquid; ¹H NMR (CDCl3, 400 MHz):  2.16 (s, 3H), 3.76 (m, 2H), 3.46 (m, 2H), 5.79 (brs, 2H), 7.41 (d, 1H, J = 8.4 Hz), 7.67 (dd, 1H, J = 6.4 Hz, J = 2.4 Hz), 8.0 (d, 1H, J = 2.0 Hz); ¹³C NMR (CDCl3, 100 MHz):  34.2, 40.6, 68.9, 118.3, 119.5, 125.6, 131.1, 140.3, 150.9, 167.4; IR (neat): 3310, 3131, 2964, 2922, 1621, 1531, 1461, 1307, 1278, 1190, 1109, 904, 822, 732 cm^-1; Anal. Calcd.

S NH CN

H₃C

S S

Me

S NH CN

H₃C

S S

NH₂

S N

NH₂ H₃C

S S

for C₁₁H₁₂N₂S₃: C, 49.22; H, 4.50; N, 10.43; S, 35.83; found: C, 49.29; H, 4.46; N, 10.39; S, 35.72.

2-Bromo-phenyl cyanamide (1a’’):

White solid, mp 95 ^oC (Lit. 94.5 ^oC²³); ¹H NMR (CDCl3, 400 MHz):  6.36 (brs, 1H), 6.96-7.01 (m, 1H), 7.25-7.39 (m, 2H) 7.52-7.53 (m, 1H); ¹³C NMR (CDCl3, 100 MHz):  109.9, 110.0, 116.1, 124.9, 129.2, 133.0, 135.3; IR (KBr): 3150, 2237, 1602, 1504, 1425, 1286, 1026, 738 cm^-1; Anal. Calcd. for C7H5BrN2: C, 42.67; H, 2.55; N, 14.21; found: C, 42.61; H, 2.62; N, 14.11.

2-Chloro-phenyl cyanamide (1’’’a):

White solid, mp 101-103 ^oC (Lit. 101-103 ^oC²²); ¹H NMR (CDCl3, 400 MHz):

 6.56 (brs, 1H), 7.05 (m, 1H), 7.31 (m, 2H), 7.35 (m, 1H); ¹³C NMR (CDCl3, 100 MHz):  110.0, 116.2, 120.4, 124.5, 128.6, 129.9, 134.3; IR (KBr): 3163, 2921, 2243, 1598, 1500, 1426, 1295, 1049, 746 cm^-1; Anal. Calcd. for C7H5ClN2: C, 55.10; H, 3.30; N, 18.36; found: C, 55.11; H, 3.32; N, 18.29.

2-Bromo-4-methyl-phenyl cyanamide (2f):

Brown solid, mp 91-92 ^oC (Lit. 91-93 ^oC²³); ¹H NMR (CDCl₃, 400 MHz):

2.31 (s, 3H), 6.23 (s, 1H), 7.14-7.19 (m, 2H) 7.34 (s, 1H); ¹³C NMR (CDCl₃, 100 MHz):  20.5, 109.6, 110.4, 115.9, 129.8, 132.7, 133.2, 135.0; IR (KBr):

3211, 2923, 2226, 1608, 1509, 1424, 1287, 1038, 863, 804, 743 cm^-1; Anal. Calcd. for C₈H₇BrN₂: C, 45.52; H, 3.34; N, 13.27; found: C, 45.61; H, 3.29; N, 13.20.

2-Bromo, 4-Methoxy phenyl cyanamide (3f):

White solid, mp 107-111 ^oC; ¹H NMR (CDCl3, 400 MHz): δ 2.9 (s, 3H), 5.28 (brs, 1H), 6.92 (dd, J1 = 6.0 Hz, J2 = 2.8 Hz, 1H), 7.08 (d, J = 2.8 Hz, 1H), 7.22 (d, J = 8.8 Hz, 1H); ¹³C NMR (CDCl3, 100 MHz): δ 56.01, 104.1, 115.2, 122.8, 130.06, 130.3, 135.1, 157.4; IR (KBr): 3287, 2925, 2251, 2220, 1611, 1507, 1399, 1286, 1218, 1036, 870, 794cm^-1; Anal. Calcd. for C8H7BrN2O: C, 42.31; H, 3.10; N, 12.34; found: C, 42.28; H, 3.15; N, 12.31.

Br HN N

Cl HN N

HN

MeO Br

N HN

Me Br

N

Phenyl cyanamide (6a):

Gummy; ¹H NMR (CDCl₃, 400 MHz):  7.02-7.07 (m, 3H), 7.28-7.33 (m, 2H), 7.64 (brs, 1H); ¹³C NMR (CDCl₃, 100 MHz):  112.2, 115.5, 123.6, 129.8, 137.4; IR (KBr): 3175, 2919, 2227, 1600, 1501, 1249, 891, 748 cm^-1; Anal. Calcd. for C₇H₆N₂: C, 71.16; H, 5.12; N, 23.71; found: C, 71.27; H, 5.09; N, 23.67.

p-Tolyl cyanamide (7a):

Gummy; ¹H NMR (CDCl3, 400 MHz):  s, 3Hd, 2H, J = 8.4 Hz7.10 (d, 2H, J = 8.4 Hz); ¹³C NMR (CDCl3, 100 MHz): 

; IR (KBr): 3165, 2950, 2228, 1620, 1515, 1249, 809 cm^-1; Anal. Calcd. for C8H8N2: C, 72.70; H, 6.10; N, 21.19; found: C, 72.27; H, 5.99; N 21.15.

4-Methoxy-phenyl cyanamide (8a):

White solid, mp 86-89 ^oC (Lit. 86-89 ^oC²³); IR (KBr): ν = 3180, 2926, 2218, 1509, 1295, 1238, 1105, 1037, 826, 795 cm^-1; ¹H NMR (CDCl3, 400 MHz):

 = 3.78 (s, 3H), 6.87 (d, 2H, J = 8.8 Hz), 6.95 (d, 2H, J = 8.8 Hz); ¹³C NMR (CDCl₃, 100 MHz):  = 55.8, 112.8, 115.2, 117.0, 130.6, 156.1; Anal. Calcd. for C₈H₈N₂O: C, 64.85; H, 5.44; N, 18.91; found: C, 64.91; H; 5.40; N, 18.93.

4-Hydroxy-phenyl cyanamide (9a):

White solid, mp 259-260 ^oC (Lit. 259-261 ^oC²²); IR (KBr): ν = 3213, 2992, 2230, 1613, 1519, 1444, 1258, 1224, 815 cm^-1; ¹H NMR (CDCl3 / DMSO- d₆, 400 MHz,): δ = 5.67 (brs, 1H), 6.77 (d, 2H, J = 8.8 Hz), 6.83 (d , 2H, J = 8.8 Hz), 8.98 (brs, 1H); ¹³C NMR (CDCl3 / DMSO-d6, 100 MHz,): δ = 112.8, 115.6, 115.8, 129.5, 152.2; Anal. Calcd for C7H6N2O: C, 62.67; H, 4.50; N, 20.89; found: C, 62.72; H, 4.55;

N, 20.83.

HN N

Me

HN N

MeO

HN N

HO

HN N

2, 4-Dimethyl-phenyl cyanamide (10a):

White solid, mp 117-119 ^oC (Lit. 115-119 ^oC²²); IR (KBr): ν = 3186, 2915, 2233, 1599, 1512, 1433, 1271, 1031, 812 cm^-1; ¹H NMR (CDCl₃, 400 MHz): 2.18 (s, 3H), 2.26 (s, 3H), 6.74 (brs, 1H), 6.93 (s, 1H), 6.99 (d, 1H, J = 8.0 Hz), 7.05 (d, 1H, J = 8.0 Hz); ¹³C NMR (CDCl3, 100 MHz): 17.3, 20.7, 112.8, 115.7, 124.7, 127.9, 131.8, 133.2, 133.3; Anal. Calcd. for C₉H₁₀N₂: C, 73.94; H, 6.89; N, 19.16;

found: C, 73.87; H, 6.86; N, 19.14.

4-Chloro-phenyl cyanamide (11a):

White solid, mp 96 ^oC (Lit. 95 ^oC²²); IR (KBr): ν = 3166, 2954, 2234, 1600, 1494, 1399, 1251, 1091, 1011, 820 cm^-1; ¹H NMR (CDCl3, 400 MHz):  = 6.91 (d, 2H, J = 8.0 Hz), 7.28 (d, 2H, J = 8.0 Hz); ¹³C NMR (CDCl3, 100 MHz):  = 111.4, 116.9, 128.9, 129.9, 136.2; Anal. Calcd. for C₇H₅ClN₂: C, 55.10; H, 3.30; N, 18.36; found: C, 55.09; H, 3.33; N, 18.32.

4-Bromo-phenyl cyanamide (12a):

White solid, mp 110-111 ^oC (Lit. 112 ^oC); IR (KBr): ν = 3153, 3078, 2958, 2884, 2228, 1594, 1503, 1493, 1394, 1281, 1251, 1073, 813 cm^-1; ¹H NMR (CDCl₃, 400 MHz): δ = 6.90 (d, 2H, J = 8.4 Hz), 7.11 (brs, 1H), 7.43 (d, 2H, J = 8.4 Hz); ¹³C NMR (CDCl₃, 100 MHz):  = 111.2, 116.4, 117.2, 132.8, 136.5; Anal. Calcd.

for C₇H₅BrN₂: C, 42.67; H, 2.55; N, 14.21; found: C, 42.61; H, 2.62; N, 14.11. (Lit 12a C.-Y.

Chen, F. F. Wong, , J.-J. Hwang, S.-K. Lin, M.-Y. Yeh, Tetrahedron Lett. 2008, 49, 6505

4-Acetyl-phenylcyanamide (13a):

White solid, mp 153-157 ^oC (Lit. 153-157 ^oC ²²); IR (KBr): ν = 3188, 2966, 2228, 1666, 1599, 1585, 1411, 1362, 1278, 1176, 962, 830 cm^-1;

1H NMR (CDCl3 / DMSO-d6, 400 MHz,): δ = 2.56 (s, 3H), 7.08 (d, 2H, J = 8.8 Hz), 7.91 (d, 2H, J = 8.8 Hz); ¹³C NMR (CDCl3 / DMSO-d6, 100 MHz,): δ = 25.9, 110.9, 114.5, 129.8, 131.2, 142.9, 196.2; Anal. Calcd. for C9H8N2O: C, 67.49; H, 5.03; N, 17.48; found:

C, 67.53; H, 5.08; N, 17.44.

HN Me

Me

N

Cl

HN N

Br

HN N

HN N H₃C

O

3-Nitro-phenyl cyanamide (14a):

Yellow solid, mp 134-136 ^oC (Lit. 133-135 ^oC²³); IR (KBr): ν = 3147, 2919, 2241, 1621, 1531, 1354, 1260, 1071, 937, 871, 733 cm^-1; ¹H NMR (CDCl₃ / DMSO-d₆, 400 MHz): δ = 7.38 (d, 1H, J = 8.4 Hz), 7.52 (t, 1H, J = 8.4 Hz), 7.85 (m, 2H); ¹³C NMR (CDCl₃ / DMSO-d₆, 100 MHz,): δ = 109.6, 110.7, 116.8, 120.8, 130.1, 139.9, 148.4; Anal. Calcd. for C₇H₅N₃O₂: C, 51.54; H, 3.09; N, 25.76; found: C, 51.58; H, 3.12; N, 25.70.

3-Trifluoromethyl phenyl cyanamide (15a):

White solid, mp 82-85 ^oC; IR (KBr): ν = 3116, 2998, 2928, 2240, 1620, 1490, 1332, 1165, 1130, 877, 794, 695 cm^-1; ¹H NMR (CDCl3, 400 MHz):  = 6.97 (brs, 1H), 7.21-7.26 (m, 2H), 7.36 (d, 1H, J = 8.0 Hz), 7.48 (t, 1H, J = 8.0 Hz);

13C NMR (CDCl3, 100 MHz): 111.1, 112.5, 118.7, 120.5, 122.3, 125.0, 130.6, 132.2, 132.5, 132.9, 138.1; Anal. Calcd. for C8H5F3N2: C, 51.62; H, 2.71; N, 15.05;

found: C, 51.54; H, 2.69; N, 15.01.

Cyclohexyl-cyanamide (16a):

Gummy; IR (KBr): ν = 3196, 2933, 2857, 2217, 1453, 1367, 1167, 892 cm^-

1; ¹H NMR (CDCl₃, 400 MHz): 1.31 (m, 5H), 1.61 (m, 1H), 1.78 (m, 2H), 1.95 (m, 2H), 3.09 (m, 1H), 3.91 (brs, 1H); ¹³C NMR (CDCl₃, 100 MHz): 24.3, 25.1, 32.6, 54.3, 115.9; Anal. Calcd. for C₇H₁₂N₂: C, 67.70; H, 9.74; N, 22.56; found: C, 67.67; H, 9.70; N, 22.50.

Benzyl cyanamide (17a):

Gummy; IR (KBr): ν = 3207, 2925, 2220, 1455, 1359, 1155, 1014,735,698 cm^-1; ¹H NMR (CDCl₃, 400 MHz): δ = 4.11 (d, J = 5.2 Hz, 2H, CH₂), 4.66 (brs, 1H), 7.27-7.37 (m, 5H); ¹³C NMR (CDCl3, 100 MHz): δ = 49.9, 116.7, 127.9, 128.4, 128.9, 136.4; Anal. Calcd. for C8H8N2: C, 72.70; H, 6.10; N, 21.19; found: C, 72.66; H, 6.13; N, 21.11.

NO₂ HN N

CF₃

HN N

HN N

HN CN

Benzoyl cyanamide (18a):

White solid, mp 135-137 ^oC (Lit. 132-136 ^oC); IR (KBr): ν = 3242, 2254, 1678, 1602, 1504, 1463, 1268, 1001, 890, 706 cm^-1; ¹H NMR (CDCl₃, 400 MHz): t, 2H, J = 7.6 Hzt, 1H, J = 7.6 Hzd, 2H, J = 7.2 Hz ¹³C NMR (CDCl3, 100 MHz): 108.6, 128.5, 128.8, 130.2, 133.8, 166.9; Anal. Calcd.

for C₈H₆N₂O: C, 65.74; H, 4.13; N, 19.17; found: C, 65.63; H, 4.18; N, 19.09. (Lit. 18a R.

Ketcham, E. Schaumann, J. Org. Chem. 1980, 45, 3748.)

NH O

N