Spectral Data

II. Regioselective Intramolecular Arylthiolations by Ligand Free Cu and Pd Catalyzed Reaction

II.8. Spectral Data

2-Morpholinobenzo[d]thiazole (1a):

White solid; Rf = 0.55 (EtOAc : hexane (2:8); M.p. 120122 ^oC (Lit.^58,60 119120 ^oC); ¹H NMR (400 MHz, CDCl3):  3.59 (t, 4H, J = 4.4 Hz), 3.80 (t, 4H., J = 4.4 Hz), 7.07 (t, 1H, J = 7.6 Hz), 7.28 (t, 1H, J = 8.0 Hz)7.57 (dd, 1H, J₁ = 6.4 Hz, J₂ = 4.0 Hz); ¹³C NMR (100 MHz, CDCl₃):  48.5, 66.2, 119.4,120.8, 121.7, 126.1, 130.6, 152.5, 169.0 IR (KBr): 2918, 2854, 1591, 1537, 1441, 1377, 1289, 1229, 1113, 1067, 1032, 945, 859, 756 cm^-1; Anal. Calcd for C₁₁H₁₂N₂OS: C, 59.97; H, 5.49; N, 12.72;

S, 14.56; Found C, 60.07; H, 5.55; N, 12.62; S, 14.48.

2-(Piperidin-1-yl)benzo[d]thiazole (1b):

White solid; R_f = 0.50 (EtOAc : hexane (2:8); M.p. 9697 ^oC (Lit.^102-103 93

oC) [(102) Yella, R; Patel, B. K. Org. Biomol. Chem., 2010, 8, 3389. (103) Jordan, A. D.; Luo, C.; Reitz, A. B. J. Org. Chem. 2003, 68, 8693)]; ¹H NMR (400 MHz, CDCl3):  1.67 (s, 6H), 3.58 (s, 4H), 7.03 (t, 1H, J = 8.0 Hz), 7.26 (t, 1H, J = 8.0 Hz), 7.55 (dd, 2H, J1 = 8.0 Hz, J2 = 5.2 Hz); ¹³C NMR (100 MHz, CDCl3):  24.3, 25.4, 49.7, 118.9, 120.7, 121.1, 126.0, 130.8, 153.1, 169.0; IR (KBr): 2934, 2922, 2849, 1588, 1534, 1440, 1382, 1332, 1257, 1234, 1209, 1120, 1006, 760 cm^-1; Anal. Calcd for C12H14N2S: C, 66.02; H, 6.46; N, 12.83; S, 14.69; found C, 66.08; H, 6.50; N, 12.76; S, 14.55.

2-(4-Benzylpiperidin-1-yl)benzo[d]thiazole (1c):

White solid; R_f = 0.5 (EtOAc : hexane (2:8); M.p. 113115 ^oC; ¹H NMR (400 MHz, CDCl₃):  1.37 (m, 1H), 1.77 (d, 4H, J = 10.8 Hz), 2.59 (d, 2H, J = 7.2 Hz), 3.06 (t, 2H, J = 12.8 Hz), 4.15 (d, 2H, J = 13.2 Hz), 7.08 (t, 1H, J = 8.0 Hz), 7.18 (d, 2H, J = 8.0 Hz), 7.26 (d, 1H, J = 7.2 Hz), 7.32 (m, 3H), 7.60 (t, 2H, J = 6.4 Hz); ¹³C NMR (100 MHz, CDCl3):  31.5, 38.0, 43.0, 49.0, 118.9, 120.7, 121.2, 126.0, 126.2, 128.4, 129.2, 130.8, 139.9, 153.0, 168.7; IR (KBr): 3061, 3024,2937, 2920, 2851, 1595, 1539, 1492, 1444, 1388, 1324, 1278, 1258, 1172, 922, 752, 727 cm^-1; HRMS (ESI) calcd for C₁₉H₂₀N₂S(M + H⁺) 309.0955; found 309.0959.

S N

N O

S N

N

S N

N

2-Thiomorpholinobenzo[d]thiazole (1d):

Yellow gum; Rf = 0.45 (EtOAc : hexane (2:8); ¹H NMR (400 MHz, CDCl₃):  2.71 (t, 4H, J = 5.2 Hz), 3.93 (t, 4H, J = 4.8), 7.06 (t, 1H, J = 7.2 Hz), 7.28 (t, 1H, J = 8.0 Hz), 7.52 (d, 1H, J = 8.0 Hz), 7.57 (d, 1H, J = 7.6 Hz); ¹³C NMR (100 MHz, CDCl3): 26.7, 51.3, 119.2, 120.8, 121.6, 126.2, 130.8, 152.7, 168.2; IR (KBr): 3059, 2936, 2858, 1599, 1531, 1444, 1385, 1359, 1313, 1218, 1054, 1020, 899, 750 cm^-1; Anal. Calcd for C₁₁H₁₂N₂S₂: C, 55.90; H, 5.12; N, 11.85; S, 27.13; found C, 55.94; H, 5.19; N, 11.77; S, 26.97.

2-(Pyrrolidin-1-yl)benzo[d]thiazole (1e):

White solid; Rf = 0.50 (EtOAc : hexane (2:8); M.p. 101–103 ^oC (Lit.¹⁰² 101

oC); ¹H NMR (400 MHz, CDCl3):  2.04 (m, 4H), 3.57 (s, 4H), 7.02 (t, 1H, J = 7.6 Hz), 7.26 (t, 1H, J = 8.0 Hz), 7 57 (t, 2H, J = 8.0 Hz); ¹³C NMR (100 MHz, CDCl3):  25.8, 48.8, 118.8, 120.8, 121.2, 126.1, 130.6, 153.1, 165.6; IR (KBr): 2924, 2851, 1604, 1544, 1442, 1363, 1314, 1278, 1166, 1119, 853 cm^-1; Anal. Calcd for C11H12N2S: C, 64.67; H, 5.92; N, 13.61; S, 15.66; found C, 64.70; H, 5.96; N, 13.68; S, 15.73.

2-(4-Cyclohexylpiperazin-1-yl)benzo[d]thiazole (1f):

White solid; R_f = 0.55 (EtOAc : hexane (2:8); Mp. 129–131 ^oC; ¹H NMR (400 MHz, CDCl₃):  1.16 (m, 6H), 1.75 (m, 5H), 2.62 (t, 4H, J = 4.4 Hz), 3.56 (t, 4H, J = 4.4 Hz), 6.99 (t, 1H, J = 7.6 Hz), 7.21 (t, 1H, J = 8.0 Hz), 7.47 (d, 1H, J = 8.0 Hz), 7.51 (d, 1H, J = 7.6 Hz); ¹³C NMR (100 MHz, CDCl3):  26.0, 26.4, 29.0, 48.5, 49.0, 63.8, 119.1, 120.8, 121.5, 126.1, 130.8, 152.9, 168.9; IR (KBr): 2922, 2851, 2814, 1595, 1541, 1443, 1387, 1341, 1250, 1125, 1016, 748 cm^-1; HRMS (ESI) calcd for C₁₇H₂₃N₃S(M + H)⁺ 302.1611; found 302.1617.

2-(4-Phenylpiperazin-1-yl)benzo[d]thiazole (1g):

White solid; Rf = 0.40 (EtOAc : hexane (2:8); M.p. 168–170 ^oC (Lit.⁶² 162163 ^oC); ¹H NMR (400 MHz, CDCl3):  3.29 (t, 4H, J

= 5.2 Hz), 3.78 (t, 4H, J = 5.2 Hz), 6.94 (m, 3H), 7.10 (t, 1H, J = 8.0 Hz), 7.33 (m, 3H), 7.62 (d, 2H, J = 8.0 Hz); ¹³C NMR (100 MHz, CDCl₃):  48.4, 49.1,

S N

N S

S N

N

S N

N N

S N

N N

116.9, 119.3, 120.7, 120.8, 121.7, 126.2, 129.3, 130.9, 151.0, 152.8, 168.7; IR (KBr): 3026, 2861, 1594, 1560, 1539, 1503, 1443, 1384, 1347, 1293, 1249, 1229, 1194, 1158, 1024, 935, 755 cm^-1; HRMS (ESI) calcd for C₁₇H₁₇N₃S(M + H⁺) 296.1154; found 296.1154.

N, N-Diethylbenzo[d]thiazole-2-amine (1h):

Gummy; Rf = 0.45 (EtOAc : hexane (2:8); ¹H NMR (400 MHz, CDCl3):  1.26 (m, 6H), 3.55 (m, 4H), 7.03 (t, 1H, J = 8.0 Hz), 7.27 (t, 1H, J = 8.0 Hz), 7.57 (m, 2H); ¹³C NMR (100 MHz, CDCl3):  12.9, 45.4, 118.5, 120.5, 120.7, 125.8, 130.6, 153.3, 167.3; IR (KBr): 3056, 2972, 2931, 2862, 1596, 1561, 1542, 1444, 1360, 1315, 1260, 1135, 1079, 1013, 750 cm^-1; HRMS (ESI) calcd for C11H14N2S(M + H)⁺ 207.0687; found 207.0687.

6-Methyl-2-morpholinobenzo[d]thiazole (2a):

White solid; R_f = 0.50 (EtOAc : hexane (2:8); M.p. 134136 ^oC (Lit.¹⁰³ 133134 ^oC); ¹H NMR (400 MHz, CDCl₃):  2.37 (s, 3H), 3.56 (t, 4H, J = 4.8 Hz), 3.79 (t, 4H, J = 4.8 Hz), 7.09 (d, 1H, J = 8.0 Hz), 7.39 (s, 1H), 7.44 (d, 1H, J = 8.0 Hz); ¹³C NMR (100 MHz, CDCl₃):  21.3, 48. 6, 66.3, 119.0, 120.9, 127.4, 130.7, 131.6, 150.4, 168.6; IR (KBr): 2963, 2912, 2856, 1599, 1575, 1544, 1464, 1434, 1352, 1281, 1235, 1113, 1026, 943, 811 cm^-1; HRMS (ESI) calcd for C₁₂H₁₄N₂OS (M + H)⁺ 235.1035; found 235.1035.

6-Butyl-2-morpholinobenzo[d]thiazole (3a):

White solid; R_f = 0.5 (EtOAc : hexane (2:8); M.p. 61–63 ^oC; ¹H NMR (400 MHz, CDCl3):  0.90 (t, 3H, J = 7.6 Hz), 1.33 (m, 2H), 1.58 (m, 2H), 2.61 (t, 2H, J = 8.0 Hz), 3.52 (t, 4H, J = 4.4 Hz), 3.74 (t, 4H, J = 4.4 Hz), 7.09 (d, 1H, J = 8.0 Hz), 7.38 (s, 1H), 7.47 (d, 1H, J = 8.0 Hz); ¹³C NMR (100 MHz, CDCl3):  13.9, 22.2, 33.9, 35.4, 48.4, 66.1, 118.9, 120.1, 126.6, 130.6, 136.5, 150.5, 168.4; IR (KBr): 2953, 2920, 2856, 1538, 1462, 1375, 1340, 1290, 1231, 1110, 1072, 1032, 944, 877, 822, 658 cm^-1; HRMS (ESI) calcd for C15H20N2SO(M + H)⁺ 277.0684; found 277.0687.

S N

N

S N

N O

Me

S N

N O

6-Fluoro-2-morpholinobenzo[d]thiazole (4a):

White solid; R_f = 0.42 (EtOAc : hexane (2:8); M.p. 157158 ^oC (Lit.⁶² 146147.5 ^oC); ¹H NMR (400 MHz, CDCl₃):  3.51 (t, 4H, J = 4.8 Hz), 3.75 (t, 4H, J = 4.4 Hz), 6.97 (m, 1H), 7.25 (m, 1H), 7.44 (m, 1H); ¹³CNMR (100 MHz, CDCl₃):

 48.4, 66.1, 107.4, 107.6, 113.6, 113.9, 119.7, 119.8, 131.2, 131.4, 148.9, 157. 0, 159.4, 168.5;

IR (KBr): 2982, 2901, 2863, 1673, 1597, 1538, 1459, 1376, 1343, 1287, 1234, 1181, 1111, 1073, 1029, 948, 920, 844 cm^-1; HRMS (ESI) calcd for C11H11N2OS F (M + H)⁺ 239.0655; found 239.0662.

2-(4-Benzylpiperidin-1-yl)-6-fluorobenzo[d]thiazole (4c):

White solid; Rf = 0.43 (EtOAc : hexane (2:8); M.p. 108109

oC; ¹H NMR (400 MHz, CDCl3):  1.34 (m, 2H), 1.77 (m, 3H), 2.57 (d, 2H, J = 6.8 Hz), 3.03 (m, 2H), 4.06 (m, 2H), 7.02 (m, 1H), 7.17 (m, 2H), 7.29 (m, 4H), 7.48 (m, 1H); ¹³C NMR (100 MHz, CDCl₃):  31.4, 37.9, 42.9, 48.9, 107.2, 107.5, 113.3, 113.6, 119.2, 119.3, 126.1, 128.3, 129.1, 131.4, 131.6, 139.8, 149.4, 156.1, 159.1, 168.2; IR (KBr): 2924, 2850, 1606, 1545, 1457, 1380, 1327, 1240, 1155, 1097, 1053, 963, 817, 744 cm^-1; HRMS (ESI) calcd for C19H19N2SF (M + H)⁺ 327.3331;

found 327.3329.

2-(4-Benzylpiperidin-1-yl)-4,6-difluorobenzo[d]thiazole (4′c):

White solid; R_f = 0.45 (EtOAc : hexane (2:8); M.p. 123124

oC; ¹H NMR (400 MHz, CDCl3):  1.36 (m, 3H), 1.79 (m, 2H), 2.58 (d, 2H, J = 6.8 Hz), 3.06 (m, 2H), 4.10 (m, 2H), 6.80 (t, 1H, J = 7.2 Hz), 7.08 (d, 1H, J = 8.0 Hz), 7.14 (d, 2H, J = 7.2 Hz), 7.21 (d, 1H, J = 7.6 Hz), 7.29 (t, 2H, J = 7.2 Hz); ¹³C NMR (100 MHz, CDCl3):  31.1, 37.5, 42.5, 48.7, 100.8, 101.1, 101.3, 102.9, 103.2, 116.5, 125.8, 128.1, 128.9, 133.1, 139.6, 150.7, 153.0, 156.2, 158.1, 167.9;

IR (KBr): 3085, 3021, 2923, 2851, 1621, 1557, 1455, 1386, 1358, 1264, 1168, 1107, 1050, 992, 929, 828, 744,701 cm^-1; HRMS (ESI) calcd for C19H18N2S F2 (M + H)⁺ 345.1315; found 345.1312.

S N

N O

F

S N

N F

S N

N F

F

6-Bromo-2-morpholinobenzo[d]thiazole (5a):

White solid; R_f = 0.43 (EtOAc : hexane (2:8); M.p. 165167 ^oC; ¹H NMR (400 MHz, CDCl₃):  3.57 (t, 4H, J = 4.8 Hz), 3.80 (t, 4H, J = 4.8 Hz), 7.37 (s, 2H), 7.68 (s, 1H); ¹³CNMR (100 MHz, CDCl3):  48.5, 66.3, 114.0, 120.5, 123.3, 129.4, 132.4, 151.6, 169.1; IR (KBr): 2918, 2857, 1591, 1535, 1443, 1372, 1280, 1258, 1229, 1110, 1026, 940, 863, 813cm^-1. Anal. Calcd for C11H11N2OSBr:

C, 44.16; H, 3.71; N, 9.36; S, 10.72; found C, 44.23; H, 3.76; N, 9.28; S, 10.64.

2-Morpholinobenzo[d]thiazole-6-carbonitrile (6a):

White solid; Rf = 0.30 (EtOAc : hexane (2:8); M.p. 173175^oC; ¹H NMR (400 MHz, CDCl3):  3.57 (t, 4H, J = 4.8 Hz), 3.74 (t, 4H, J = 4.4 Hz), 7.42 (s, 2H), 7.75 (s, 1H);.¹³C NMR (100 MHz, CDCl₃):  48.5, 66.0, 103.9, 119.2, 124.9, 130.0, 131.1, 155.9, 162.5, 171.0; IR (KBr): 2906, 2861, 2224, 1526, 1554, 1434, 1325, 1286, 1226, 1194, 1118, 1067, 1028, 949, 838 cm^-1. HRMS (ESI) calcd for C12H11N3OS(M + H)⁺ 246.0702; found 246.0649.

6-(Trifluoromethyl)-2-morpholinobenzo[d]thiazole (7a):

White solid; R_f = 0.35 (EtOAc : hexane (2:8); Mp 118120 ^oC; ¹H NMR (400 MHz, CDCl3):  3.57 (t, 4H, J = 4.8 Hz), 3.76 (t, 4H, J = 4.4 Hz), 7.48 (d, 1H, J = 8.4 Hz), 7.53 (d, 1H, J = 8.4 Hz, 7.80 (s, 1H); ¹³C NMR (100 MHz, CDCl₃): 48.5, 66.1, 118.2, 118.3, 119.0, 123.3, 123.4, 123.7, 126.0, 131.8, 155.2, 170.5 ¹⁹F NMR (CDCl3 + Hexafluoro Benzene);  100.7 (s); IR (KBr): 2973, 2949, 2921, 2898, 2863, 1571, 1541, 1378, 1321, 1291, 1232, 1161, 1115, 1085, 944, 832 cm^-1; HRMS (ESI) calcd for C12H11F3N2OS(M + H⁺) 289.0629; found 289.0631.

2-Morpholino-5-nitrobenzo[d]thiazole (8a):

Yellow solid; Rf = 0.35 (EtOAc : hexane (2:8); M.p. 172174 ^oC; ¹H NMR (400 MHz, CDCl3):  3.60 (t, 4H, J = 4.8 Hz), 3.82 (t, 4H, J = 4.4 Hz), 7.64 (d, 1H, J = 8.4 Hz), 7.91 (d, 1H, J = 8.8 Hz), 8.29 (s, 1H); ¹³C NMR (100 MHz, CDCl₃):  48.5, 66.1, 113.9, 116.2, 120.8, 137.9, 146.9, 153.0,   170.3; IR (KBr):

S N

N O

Br

S N

N O

NC

S N

N O

F₃C

N S

N O

O₂N

3095, 2972, 2914, 2865, 1602, 1579, 1528, 1508, 1449, 1428, 1343, 1282, 1233, 1119, 1068, 1022, 896, 873, 816 cm^-1; Anal. Calcd for C11H11N3O3S: C, 49.80; H, 4.18; N, 15.84; S, 12.09;

found C, 49.83; H, 4.20; N, 15.82; S 12.12.

5-Chloro-2-morpholinobenzo[d]thiazole (9a):

White solid; R_f = 0.40 (EtOAc : hexane (2:8); M.p. 122124 ^oC ¹H NMR (400 MHz, CDCl₃):  3.56 (t, 4H, J = 4.8 Hz), 3.81 (t, 4H, J = 4.8 Hz), 7.18 (dd, 1H, J1 = 8.4Hz, J2 = 2.0 Hz), 7.43 (d, 1H, J = 8.4 Hz), 7.69 (d, 1H, J = 2.0 Hz); ¹³C NMR (100 MHz, CDCl₃):  48.5, 66.2, 119.3, 121.5, 121.8, 128.9, 132.0, 153.7, 170.1; IR (KBr): 3051, 2978, 2902, 2855, 1737, 1587, 1530, 147, 1375, 1325, 1279, 1234, 1142, 1116, 1070, 1035, 885, 872, 808, 678 cm^-1; HRMS (ESI) calcd for C₁₁H₁₁N₂OSCl(M + H)⁺ 255.0446; found 255.0446.

5-Bromo-2-morpholinobenzo[d]thiazole (10a):

White solid; Rf = 0.45 (EtOAc : hexane (2:8); M.p. 118120 ^oC; ¹H NMR (400 MHz, CDCl3):  3.56 (t, 4H, J = 4.8 Hz), 3.78 (t, 4H, J = 4.8 Hz), 7.01 (d, 1H, J = 8.4 Hz), 7.44 (d, 1H, J = 8.4 Hz), 7.50 (s 1H); ¹³C NMR (100 MHz, CDCl3):  48.6, 66.3, 120.9, 121.9, 122.3, 124.6, 129.5, 154.1, 169.9;

IR (KBr): 2924, 2853, 1526, 1443, 1338, 1230, 1110, 1068, 1030, 876, 800 cm^-1; HRMS (ESI) calcd for C11H11N2OSBr(M + H)⁺ 300.9868; found 300.9870.

6,6-Dimethyl-2-morpholinobenzo[d]thiazole (11a):

White solid; Rf = 0.55 (EtOAc : hexane (2:8); M.p. 156–158 ^oC; ¹H NMR (400 MHz, CDCl₃):  2.27 (s, 3H), 2.28 (s, 3H), 3.55 (t, 4H, J = 4.4 Hz), 3.79 (t, 4H, J = 4.4 Hz), 7.34 (s, 1H), 7.36 (s, 1H); ¹³C NMR (100 MHz, CDCl3):  19.9, 20.2, 48.6, 66.4, 120.3, 121.2, 127.9, 130.7, 134.9, 151.0, 168.8; IR (KBr): 2966, 2916, 2857, 1612, 1537, 1444, 1375, 1343, 1283, 1227, 1140, 1114, 1069, 1042, 1020, 994, 899, 858 cm^-1; HRMS (ESI) calcd for C₁₃H₁₆N₂OS: (M + H)⁺ 249.1161; found 249.1164.

N S

N O

Cl

S N

N O

Br

S N

N O

Me Me

2-Morpholinonaptho[1,2-d]thiazole (12a):

Pinkish solid; R_f = 0.5 (EtOAc : hexane (2:8); M.p 183184 ^oC (Lit.⁹³ 183184 ^oC); ¹H NMR (400 MHz, CDCl₃):  3.67 (t, 4H, J = 4.8 Hz), 3.86.(t, 4H, J = 4.8 Hz), 7.58 (m, 3H), 7.98 (s, 1H), 8.23 (m, 1H), 8.57 (m, 1H); ¹³CNMR (100 MHz, CDCl3):  48.7, 66.4, 114.9, 122.4, 124.6, 125.5, 126.8, 126.7, 127.5, 127.9, 130.5, 148.5, 169; IR (KBr): 2961, 2844, 1568, 1531, 1496, 1451, 1393, 1351, 1278, 1226, 1156, 1112, 1080, 1035, 910, 758cm^-1; Anal. Calcd for C15H14N2OS: C, 66.64; H, 5.22; N, 10.36; S, 11.86; found C, 66.70; H, 5.24; N, 10.27; S, 11.79.

4-Fluoro-2-morpholinobenzo[d]thiazole (13a):

White solid; Rf = 0.45 (EtOAc : hexane (2:8); M.p. 122–123 ^oC (Lit.⁵⁸ 122122.5 ^oC) ¹H NMR (400 MHz, CDCl3):  3.62 (t, 4H, J = 4.8 Hz), 3.80 (t, 4H, J = 4.8 Hz), 6.987.04 (m, 2H), 7.347.36 (m, 1H); ¹³C NMR (100 MHz, CDCl₃):  48.5, 66.2, 112.3(²J_CF = 73.2 Hz), 116.5, 122.1 (²J_CF = 23.6 Hz), 133.1, 152.2, 154.7, 169.0; ¹⁹F NMR (CDCl₃ + Hexafluoro Benzene)  35.6; IR (KBr): 2931, 2917, 2865, 1610, 1542, 1474, 1375, 1336, 1282, 12, 1121, 949, 927, 780 cm^-1; HRMS (ESI) calcd for C₁₁H₁₁N₂OSF(M + H⁺) 239.0616; found 239.0619.

4-Fluoro-2-(piperidin-1-yl)benzo[d]thiazole (13b):

White solid; Rf = 0.45 (EtOAc : hexane (2:8); M.p. 9698 ^oC; ¹H NMR (400 MHz, CDCl3):  1.61 (s, 6H), 3.54 (s, 4H), 6.886.98 (m, 2H), 7.26-7.28 (m, 1H); ¹³C NMR (100 MHz, CDCl3):  24.1, 25.3, 49.6, 111.8, 112.0, 116.2, 116.3, 121.1, 121.2, 133.3, 151.8, 154.3, 168.7; ¹⁹F NMR (CDCl3 + Hexafluoro Benzene)  35.1;

IR (KBr): 2934, 2853, 1597, 1548, 1442, 1385, 1359, 1289, 1232, 1135, 1056, 1009, 911, 855, 771 cm^-1. HRMS (ESI) calcd for C12H13N2SF (M + H)⁺ 237.0857; found 237.0857.

6-Bromo-4-fluoro-2-morpholinobenzo[d]thiazole (16a):

White solid; Rf = 0.45 (EtOAc : hexane (2:8); M.p. 103105 ^oC; ¹H NMR (400 MHz, CDCl₃):  3.61 (t, 4H, J = 4.8 Hz), 3.79 (t, 4H, J = 4.8 Hz), 6.98-7.18 (m, 1H,), 7.33746 (m, 1H); ¹³C NMR (100 MHz,

S N

N O

S N

N O

F

S N

N F

S N

N O

F

Br

CDCl₃):  48.6, 66.3, 112.2, 112.4, 116.1, 16.3, 116.6, 119.3, 122.0, 122.1, 129.4, 154.8, 169.0;

19F NMR (CDCl₃ + Hexafluoro Benzene)  35.7, 38.3; IR (KBr): 2922, 2857, 1608, 1544, 1445, 1375, 1283, 1232, 1232, 1114, 1031, 953, 805 cm^-1; HRMS (ESI) calcd for C₁₁H₁₀FBrN₂OS (M + H)⁺ 318.9728; found 318.9731.

5-Fluoro-2-morpholinobenzo[d]thiazole (17a):

White solid; Rf = 0.45 (EtOAc : hexane (2:8); M.p. 110111 ^oC; ¹H NMR (400 MHz, CDCl3):  3.50 (t, 4H, J = 4.4 Hz), 3.71 (t, 4H, J = 4.4 Hz), 6.73 (m, 1H), 7.17 (m, 1H), 7.39 (m, 1H); ¹³C NMR (100 MHz, CDCl3):  48.5, 66.2, 106.0, 106.3, 109.3, 109.5, 121.2, 121.3, 125.8, 153.8, 153.9, 161.0, 163.4, 170.7; IR (KBr): 2971, 2918, 2852, 1610, 1528, 1446, 1339, 1286, 1231, 1117, 1033, 930, 899, 874, 806, 690 cm^-1; HRMS (ESI) calcd for C11H11N2OSF (M + H)⁺ 239.0655; found 239.0662.

4,7-Difluoro-2-morpholinobenzo[d]thiazole (17′a):

White solid; R_f = 0.40 (EtOAc : hexane (2:8); M.p. 159160 ^oC; ¹H NMR (400 MHz, CDCl₃):  3.57 (t, 4H, J = 4.8 Hz), 3.75 (t, 4H, J = 4.8 Hz), 6.66 (m, 1H), 6.90 (m, 1H); ¹³C NMR (100 MHz, CDCl₃): 48.5, 66.1, 107.0, 107.1, 107.2, 107.3, 112.3, 112.4, 112.5, 112.6, 118.9, 119.1, 142.5, 142.7, 148.4, 150.9, 151.4, 153.8, 169.3; IR (KBr): 3076, 2926, 1551, 1492, 1398, 1340, 1267, 1236, 1116, 1038, 947, 806, 750 cm^-1; HRMS (ESI) calcd for C₁₁H₁₀N₂OSF₂ (M + H)⁺ 257.0579; found 257.0581.

N-(2,5-Diflurophenyl)acetamide (17i):

White solid; Rf = 0.50 (EtOAc : hexane (2:8); M.p. 131133 ^oC; ¹H NMR (400 MHz, CDCl3):  2.20 (s, 3H), 6.71 (m, 1H), 7.00 (m, 1H), 7.78 (brs, 1H), 8.12 (m, 1H); ¹³C NMR (100 MHz, CDCl3):  24.6, 108.9, 109.2, 110.0, 110.1, 110.3, 115.1, 115.2, 115.3, 115.4, 127.3, 149.6, 157.4, 159.8, 168.8. IR (KBr): 3302, 3274, 2917, 1671, 1629, 1544, 1484, 1434, 1367, 1327, 1257, 1240, 1190, 1140, 1017, 971, 872, 804, 726 cm^-1; HRMS (ESI) calcd for C8H7NOF2 (M + H)⁺ 172.0541; found 172.0539.

S N

N O

F

S N

N O

F

F

HN CH₃ O F

F

4-Chloro-2-morpholinobenzo[d]thiazole (18a):

White solid; R_f = 0.50 (EtOAc : hexane (2:8); M.p. 101102 ^oC (Lit.⁵⁸ 101-102 ^oC); ¹H NMR (400 MHz, CDCl₃):  3.57 (t, 4H, J = 4.4 Hz), 3.75 (t, 4H, J = 4.8 Hz), 6.92 (t, 1H, J = 8.0 Hz), 7.25 (d, 1H, J = 8.0 Hz), 7.41 (d, 1H, J = 8.0 Hz); ¹³C NMR (100 MHz, CDCl3):  48.5, 66.2, 119.3, 120.8, 122.0, 126.4, 131.8, 149.6, 169.0; IR (KBr): 2970, 2865, 1589, 1538, 1442, 1412, 1375, 1281, 1237, 1117, 1035, 945, 777 cm^-1; HRMS (ESI) calcd for C11H11ClN2OS (M + H)⁺ 255.0446; found 255.0449.

4-Chloro-2-(piperidin-1-yl)benzo[d]thiazole (18b):

Gummy; Rf = 0.50 (EtOAc : hexane (2:8); ¹H NMR (400 MHz, CDCl3):  1.67 (s, 6H), 3.60 (s, 4H), 6.92 (t, 1H, J = 8.0 Hz), 7.26 (d, 1H, J = 8.0 Hz), 7.43 (d, 1H, J = 8.0 Hz); ¹³C NMR (100 MHz, CDCl3):  24.4, 25.5, 49.7, 119.2, 121.2, 121.4, 126.3, 132.0, 150.1, 168.9; IR (KBr): 2935, 2853, 1589, 1537, 1446, 1415, 1249, 1212, 1106, 1015 cm^-1; Anal. Calcd for C12H13N2SCl: C, 57.02; H, 5.18; N, 11.08; S, 12.69; found C, 57.12; H, 5.26; N, 11.05; S, 12.71.

6-Chloro-2-morpholinobenzo[d]thiazole (19a):

White solid; R_f = 0.45 (EtOAc : hexane (2:8); M.p. 144145 ^oC; ¹H NMR (400 MHz, CDCl₃):  3.61 (t, 4H, J = 4.8 Hz), 3.81 (t, 4H, J = 5.2 Hz), 7.19 (dd, 1H, J₁ = 8.4 Hz, J₂ = 2.0 Hz), 7.39 (d, 1H, J = 8.8 Hz), 7.49 (d, 1H, J = 2.0 Hz); ¹³C NMR (100 MHz, CDCl3):  48.4, 66.1, 119.9, 120.4, 126.5, 126.7, 131.8, 151.2, 169.0;

IR (KBr): 2943, 2919, 2859, 1594, 1537, 1447, 1330, 1279, 1233, 1110, 1027, 940, 814 cm^-1; HRMS (ESI) calcd for C₁₁H₁₁N₂OSCl (M + H)⁺ 255.0446; found 255.0448.

4, 6-Dichloro-2-morpholinobenzo[d]thiazole (19′a):

White solid; Rf = 0.42 (EtOAc : hexane (2:8); M.p. 141142 ^oC ; ¹H NMR (400 MHz, CDCl3):  3.51 (t, 4H, J = 4.4 Hz), 3.74 (t, 4H, J = 4.8 Hz), 7.30 (d, 1H, J = 2.0 Hz), 7.43 (d, 1H, J = 2.0 Hz); ¹³C NMR (100

S N

N O

Cl

S N

N Cl

S N

N O

Cl

S N

N O

Cl Cl

MHz, CDCl₃):  48.4, 66.2, 119.1, 123.9, 126.4, 126.5, 132.4, 148.4, 168.9; IR (KBr): 3060, 2856, 1587, 1536, 1431, 1380, 1336, 1275, 1231, 1115, 1070, 1026, 942 cm^-1; HRMS (ESI) calcd for C₁₁H₁₀Cl₂N₂OS (M + H)⁺ 289.0002; found 289.0002.

2-(4-Benzylpiperidin-1-yl)-6-chlorobenzo[d]thiazole (19c):

Gummy; R_f = 0.52 (EtOAc : hexane (2:8); ¹H NMR (400 MHz, CDCl3):  1.35 (m, 3H), 1.75 (d, 2H, J = 11.2 Hz), 2.56 (d, 2H, J = 7.6 Hz), 3.05 (m, 2H), 4.07 (m, 2H), 7.13 (d, 2H, J

= 8.4 Hz), 7.19 (m, 2H), 7.28 (m, 2H), 7.39 (d, 1H, J = 8.4 Hz), 7.51 (d, 1H, J = 2.4 Hz); ¹³C NMR (100 MHz, CDCl3):  31.1, 37.5, 42.6, 48.6, 119.2, 120.0, 125.9, 126.0, 128.1, 128.9, 131.9, 139.5, 151.5, 168.4; IR (KBr): 2919, 2851, 1591, 1530, 1439, 1374, 1281, 1161, 1100, 1048, 965, 805, 699 cm^-1; HRMS (ESI) calcd for Anal. Calcd for C19H19N2SCl: C, 66.55; H, 5.92; N, 8.17; S, 9.35; found C, 66.58; H, 5.96; N, 8.21; S, 9.38.

2-(4-Benzylpiperidin-1-yl)-4,6-dichlorobenzo[d]thiazole (19′c):

Gummy; Rf = 0.52 (EtOAc : hexane (2:8); ¹H NMR (400 MHz, CDCl₃):  1.38 (m, 3H), 1.77 (m, 3H), 2.56 (d, 2H, J = 6.8 Hz), 3.06 (m, 1H), 4.09 (m, 2H), 7.15 (d, 2H, J = 7.2 Hz), 7.23 (m, 2H), 7.31 (m, 3H); ¹³C NMR (100 MHz, CDCl₃):  31.4, 37.8, 42.8, 48.9, 118.9, 120.3, 123.3, 125.6, 126.2, 128.4, 129.1, 132.7, 139.7, 148.9, 168.5; IR (KBr): 3076, 2926, 1551, 1492, 1398, 1340, 1267, 1236, 1116, 1038, 947, 806, 750 cm^-1; HRMS (ESI) calcd for C₁₉H₁₈N₂SCl₂ (M + H)⁺ 379.0649; found 379.0649.

6-Bromo-4-chloro-2-morpholinobenzo[d]thiazole (20a):

White solid; Rf = 0.45 (EtOAc : hexane (2:8); M.p. 158159 ^oC; ¹H NMR (400 MHz, CDCl3):  3.57 (t, 4H, J = 4.8 Hz), 3.77 (t, 4H, J = 4.8 Hz), 7.39 (d, 1H, J1 = 2.0 Hz), 7.52 (d, 1H, J = 2.0 Hz); ¹³C NMR (100 MHz, CDCl3):  48.4, 66.1, 113.1, 121.8, 124.2, 129.0, 132.9, 148.8, 168.8; IR (KBr):

2922, 2857, 1637, 1589, 1533, 1429, 1375, 1333, 1230, 1115, 1031, 941, 835, 635 cm^-1; HRMS (ESI) calcd for C11H10N2OSClBr (M + H)⁺ 334.9389; found 334.9384.

S N

N Cl

S N

N Cl

Cl

S N

N O

Br Cl