Scheme II.3.6. Plausible mechanism for the synthesis of 2-iminothiazolidines
II.6. Spectral data of product
N-(3-Butyl-5-phenylthiazolidin-2-ylidene)benzamide (1a)
Yellowish solid (149 mg, 88%); mp: 80− oC. 1H NMR (600 MHz, CDCl3): δ (ppm) 0.99 (t, 3H, J = 7.8 Hz), 1.42 (m, 2H), 1.69 (m, 2H), 3.71 (dd, 1H, J = 7.2, 3.0 Hz), 3.82 (t, 2H, J = 7.8 Hz), 4.01 (dd, 1H, J = 8.4, 2.4 Hz), 4.71 (t,
Chapter II 2-Iminothiazolidines 7.8 Hz), 7.39 (d, 2H, J = 7.8 Hz), 7.43 (t, 2H, J = 7.8 Hz), 7.50 (t, 1H, J = 7.2 Hz), 8.30 (d, 2H, J = 7.8 Hz); 13C{1H}
NMR (100 MHz, CDCl3): δ (ppm) 13.9, 20.2, 29.4, 46.8, 47.6, 57.3, 127.5, 128.1, 128.3, 129.1, 129.7, 132.0, 137.0, 139.5, 171.0, 175.9; IR (KBr): 3063, 2958, 2859, 1626, 1614, 1539, 1405, 1333, 1289 cm-1; HRMS (ESI): calcd.
for C20H23N2OS+ [M + H+] 339.1526; found 339.1531.
N-(3-Butyl-5-phenylthiazolidin-2-ylidene)-4-methylbenzamide(1b)
White solid (151 mg, 86%); mp: 100− oC. 1H NMR (600 MHz, CDCl3): δ (ppm) 0.99 (t, 3H, J = 7.2 Hz), 1.42 (m, 2H), 1.69 (m, 2H), 2.41 (s, 3H), 3.69 (dd, 1H, J = 7.8, 3.0 Hz), 3.81 (t, 2H, J = 7.2 Hz), 4.00 (dd, 1H, J = 8.4, 2.4 Hz), 4.71 (t, 1H, J = 7.8 Hz), 7.23 (d, 2H, J = 8.4 Hz), 7.34 (t, 3H, J = 7.2 Hz), 7.40 (d, 2H, J = 7.8 Hz), 8.19 (d, 2H, J = 7.8 Hz); 13C{1H} NMR (100 MHz, CDCl3): δ (ppm) 14.0, 20.3, 21.8, 29.4, 46.8, 47.6, 57.3, 127.6, 128.3, 128.9, 129.1, 129.8, 134.3, 139.6, 142.4, 170.8, 176.0; IR (KBr): 2957, 2925, 2856, 1611, 1538, 1407, 1247, 1169, 1017 cm-1; HRMS (ESI): calcd. for C21H25N2OS+ [M + H+] 353.1682; found 353.1687.
N-(3-Butyl-5-phenylthiazolidin-2-ylidene)-4-ethylbenzamide (1c)
Yellowish solid (154 mg, 84%); mp: 76− oC. 1H NMR (600 MHz, CDCl3): δ (ppm) 0.98 (t, 3H, J = 7.8 Hz), 1.25 (t, 3H, J = 7.2 Hz), 1.41 (m, 2H), 1.67 (m, 2H), 2.69 (q, 2H, J = 7.8 Hz), 3.68 (dd, 1H, J = 7.2, 3.6 Hz), 3.80 (t, 2H, J = 7.8 Hz), 3.98 (dd, 1H, J = 8.4, 3.0 Hz), 4.69 (t, 1H, J
= 7.8 Hz), 7.26 (t, 2H, J = 8.4 Hz), 7.29 (d, 1H, J = 7.2 Hz), 7.33 (t, 2H, J = 7.8 Hz), 7.38 (d, 2H, J = 7.2 Hz), 8.21 (d, 2H, J = 7.8 Hz); 13C{1H} NMR (100 MHz, CDCl3): δ (ppm) 13.9, 15.5, 20.2, 29.0, 29.3, 46.7, 47.5, 57.2, 127.5, 127.6, 128.2, 129.0, 129.9, 134.5, 139.5, 148.5, 170.6, 175.9; IR (KBr): 3026, 2962, 2930, 1619, 1537, 1403,
Chapter II 2-Iminothiazolidines 1288, 1170, 1016 cm-1; HRMS (ESI): calcd. for C22H27N2OS+ [M + H+] 367.1839; found 367.1835.
N-(3-Butyl-5-phenylthiazolidin-2-ylidene)-4-methoxybenzamide (1d)
Yellow solid (132 mg, 72%); mp: 88− oC. 1H NMR (600 MHz, CDCl3): δ (ppm) 0.98 (t, 3H, J = 7.8 Hz), 1.41 (d, 2H, J = 7.8 Hz), 1.68 (m, 2H), 3.68 (dd, 1H, J = 7.2, 3.6 Hz), 3.80 (t, 2H, J = 7.2 Hz), 3.85 (s, 3H), 3.98 (dd, 1H, J
= 8.4, 2.4 Hz), 4.69 (t, 1H, J = 7.8 Hz), 6.92 (d, 2H, J = 9.0 Hz), 7.29 (t, 1H, J = 7.2 Hz), 7.33 (t, 2H, J = 7.8 Hz), 7.39 (d, 2H, J = 7.2 Hz), 8.26 (d, 2H, J = 9.0 Hz); 13C{1H}
NMR (100 MHz, CDCl3): δ (ppm) 13.9, 20.2, 29.3, 46.7, 47.5, 55.5, 57.2, 113.3, 127.5, 128.2, 129.0, 129.7, 131.7, 139.6, 162.7, 170.4, 175.4; IR (KBr): 2958, 2930, 2858, 1618, 1571, 1538, 1403, 1250, 1160, 1029 cm-1; HRMS (ESI): calcd. for C21H25N2O2S+ [M + H+] 369.1631; found 369.1640.
N-(3-Butyl-5-phenylthiazolidin-2-ylidene)-4-chlorobenzamide (1e)
Yellow solid (166 mg, 89%); mp: 107− oC. 1H NMR (600 MHz, CDCl3): δ (ppm) 0.98 (t, 3H, J = 7.2 Hz), 1.41 (m, 2H), 1.66−1.71 (m, 2H), 3.72 (dd, 1H, J = 7.8, 3.6 Hz), 3.80 (t, 2H, J = 7.2 Hz), 4.02 (dd, 1H, J = 8.4, 1.8 Hz), 4.72 (t, 1H, J = 7.8 Hz), 7.31 (d, 1H, J = 7.2 Hz), 7.34 (t, 2H, J = 7.8 Hz), 7.39 (d, 4H, J = 8.4 Hz), 8.22 (d, 2H, J = 8.4 Hz); 13C{1H} NMR (150 MHz, CDCl3): δ (ppm) 13.9, 20.2, 29.4, 46.8, 47.6, 57.4, 127.5, 128.3, 128.4, 129.1, 131.2, 135.5, 138.0, 139.3, 171.2, 174.8; IR (KBr): 2962, 2926, 2856, 1623, 1537, 1411, 1322, 1242, 1117, 1062 cm-1; HRMS (ESI): calcd. for C20H22ClN2OS+ [M + H+] 373.1136; found 373.1130.
Chapter II 2-Iminothiazolidines N-(3-Butyl-5-phenylthiazolidin-2-ylidene)-4-fluorobenzamide (1f)
Yellow solid (162 mg, 91%); mp: 94− oC. 1H NMR (400 MHz, CDCl3): δ (ppm) 0.98 (t, 3H, J = 7.6 Hz), 1.38−1.44 (m, 2H), 1.65−1.70 (m, 2H), 3.71 (dd, 1H, J = 7.6, 3.6 Hz), 3.80 (t, 2H, J = 7.2 Hz), 4.01 (dd, 1H, J = 8.4, 2.8 Hz), 4.71 (t, 1H, J = 8.0 Hz), 7.08 (t, 2H, J = 8.8 Hz), 7.31 (dd, 1H, J = 8.0, 3.6 Hz), 7.37 (dd, 4H, J = 8.0, 4.8 Hz), 8.30 (dd, 2H, J = 8.4, 2.8 Hz); 13C{1H} NMR (150 MHz, CDCl3): δ (ppm) 13.9, 20.2, 29.4, 46.8, 47.6, 57.4, 115.0, 115.1, 127.5, 128.4, 129.1, 132.1, 132.2, 133.23, 133.24, 139.4, 164.5, 166.2, 171.1, 174.8; IR (KBr): 3064, 2958, 2929, 2860, 1622, 1537, 1410, 1239, 1146 cm-1; HRMS (ESI): calcd. for C20H22FN2OS+ [M + H+] 357.1431; found 357.1435.
N-(3-Butyl-5-phenylthiazolidin-2-ylidene)-4-(trifluoromethyl)benzamide (1g)
White solid (191 mg, 94%); mp: 123− oC. 1H NMR (600 MHz, CDCl3): δ (ppm) 0.99 (t, 3H, J = 8.4 Hz), 1.42 (m, 2H), 1.67−1.72 (m, 2H), 3.75 (dd, 1H, J = 7.2, 3.6 Hz), 3.83 (t, 2H, J = 7.2 Hz), 4.04 (dd, 1H, J = 8.4, 3.0 Hz), 4.75 (t, 1H, J = 7.8 Hz), 7.31 (m, 1H), 7.35 (t, 2H, J = 7.8 Hz), 7.39 (d, 2H, J = 7.2 Hz), 7.69 (d, 2H, J = 7.8 Hz), 8.38 (d, 2H, J = 8.4 Hz); 13C{1H} NMR (150 MHz, CDCl3): δ (ppm) 13.9, 20.2, 29.4, 46.9, 47.7, 57.5, 125.10, 125.12, 125.15, 125.17, 127.5, 128.5, 129.2, 130.0, 133.1, 133.3, 139.3, 140.3, 171.7, 174.6; IR (KBr): 2953, 2925, 2853, 1622, 1536, 1411, 1322, 1290, 1015 cm-1; HRMS (ESI): calcd. for C21H22F3N2OS+ [M + H+] 407.1399;
found 407.1402.
N-(3-Butyl-5-phenylthiazolidin-2-ylidene)-4-nitrobenzamide (1h)
White solid (184 mg, 96%); mp: 171− oC. 1H NMR (600 MHz, CDCl3): δ (ppm) 0.99 (t, 3H, J = 7.2 Hz),
Chapter II 2-Iminothiazolidines 7.8, 3.6 Hz), 3.84 (t, 2H, J = 7.8 Hz), 4.07 (dd, 1H, J = 8.4, 2.4 Hz), 4.77 (t, 1H, J = 7.8 Hz), 7.31 (m, 1H), 7.35 (t, 2H, J = 7.8 Hz), 7.39 (d, 2H, J = 7.2 Hz), 8.25 (d, 2H, J = 9.0 Hz), 8.40 (d, 2H, J = 9.0 Hz); 13C{1H} NMR (100 MHz, CDCl3): δ (ppm) 13.9, 20.2, 29.4, 46.9, 47.8, 57.6, 123.4, 127.5, 128.6, 129.2, 130.6, 139.1, 142.6, 149.9, 172.1, 173.8; IR (KBr): 2960, 2927, 2852, 1625, 1594, 1537, 1406, 1340, 1245, 1015 cm-1; HRMS (ESI): calcd. for C20H22N3O3S+ [M + H+] 384.1376; found 384.1380.
N-((R)-3-Butyl-5-phenylthiazolidin-2-ylidene)cinnamamide (1i)
Yellow gummy (135 mg, 74%). 1H NMR (400 MHz, CDCl3): δ (ppm) 0.99 (t, 3H, J = 7.6 Hz), 1.41 (m, 2H), 1.63−1.70 (m, 2H), 3.68 (dd, 1H, J = 7.6, 3.2 Hz), 3.76 (dd, 2H, J = 6.8, 1.2 Hz), 3.98 (dd, 1H, J = 10.5, 2.8 Hz), 4.68 (t, 1H, J = 8.0 Hz), 6.77 (d, 1H, J = 16.0 Hz), 7.30−7.40 (m, 8H), 7.57 (dd, 2H, J = 7.6, 1.6 Hz), 7.81 (d, 1H, J = 15.6 Hz); 13C{1H} NMR (100 MHz, CDCl3): δ (ppm) 13.9, 20.1, 29.3, 46.7, 47.4, 57.2, 126.7, 127.5, 128.1, 128.3, 128.8, 129.0, 129.6, 135.7, 139.4, 142.2, 170.4, 176.4; IR (KBr): 3062, 2957, 2929, 2860, 1638, 1595, 1534, 1403, 1338, 1176 cm-1; HRMS (ESI): calcd.
for C22H25N2OS+ [M + H+] 365.1682; found 365.1690.
N-(3-Butyl-5-phenylthiazolidin-2-ylidene)pent-4-enamide (1j)
Yellow gummy (109 mg, 69%). 1H NMR (400 MHz, CDCl3): δ (ppm) 0.95 (t, 3H, J = 7.6 Hz), 1.35 (m, 2H), 1.60 (dt, 2H, J = 7.2 Hz), 2.43 (t, 2H, J = 6.8 Hz), 2.56 (m, 1H), 361−3.68 (m, 3H), 3.93 (dd, 1H, J = 8.4, 2.4 Hz), 4.64 (t, 1H, J = 8.0 Hz), 4.95−5.08 (m, 3H), 5.86−5.93 (m, 1H), 7.28−7.37 (m, 5H); 13C{1H} NMR (100 MHz, CDCl3): δ (ppm) 13.9, 20.2, 29.4, 29.9, 39.5, 46.8, 47.3, 57.2, 114.6, 127.6, 128.4, 129.1, 138.7, 139.5, 169.9,
Chapter II 2-Iminothiazolidines 1019 cm-1; HRMS (ESI): calcd. for C18H25N2OS+ [M + H+] 317.1682; found 317.1685.
N-(3-Butyl-5-phenylthiazolidin-2-ylidene)cyclohexanecarboxamide (1k)
Colorless gummy (124 mg, 72%). 1H NMR (400 MHz, CDCl3): δ (ppm) 0.95 (t, 3H, J = 7.6 Hz), 1.20-1.40 (m, 7H), 1.63 (m, 3H), 1.76 (m, 2H), 1.95 (m, 2H), 2.37 (m, 1H), 3.65 (m, 3H), 3.90 (dd, 1H, J = 8.4, 2.4 Hz), 4.64 (t, 1H, J = 6.8 Hz), 7.33 (m, 5H); 13C{1H} NMR (100 MHz, CDCl3): δ (ppm) 14.0, 20.1, 26.1, 26.2, 26.4, 29.3, 29.75, 29.85, 46.9, 47.3, 48.2, 57.2, 127.7, 128.3, 129.1, 139.5, 170.0, 187.9; IR (KBr): 2927, 2855, 1631, 1534, 1403, 1245, 912 cm-1; HRMS (ESI): calcd. for C20H29N2OS+ [M + H+] 345.1995; found 345.1990.
N-(3-Butyl-5-(p-tolyl)thiazolidin-2-ylidene)benzamide (2a)
Yellow gummy (162 mg, 91%). 1H NMR (600 MHz, CDCl3): δ (ppm) 0.99 (t, 3H, J = 7.2 Hz), 1.42 (m, 2H), 1.69 (m, 2H), 2.34 (s, 3H), 3.68 (dd, 1H, J = 7.8, 3.0 Hz), 3.82 (td, 2H, J = 7.8 Hz), 3.98 (dd, 1H, J = 7.8, 2.4 Hz), 4.69 (t, 1H, J = 8.4 Hz), 7.15 (d, 2H, J = 8.4 Hz), 7.29 (t, 2H, J = 7.8 Hz), 7.43 (t, 3H, J = 7.2 Hz), 8.30 (t, 2H, J = 8.4 Hz); 13C{1H} NMR (100 MHz, CDCl3): δ (ppm) 13.9, 21.1, 21.2, 29.3, 46.5, 47.5, 57.3, 127.4, 128.0, 129.6, 129.7, 131.8, 136.2, 136.9, 138.0, 171.0, 175.8; IR (KBr):
3022, 2957, 2926, 1626, 1538, 1404, 1248, 1022 cm-1; HRMS (ESI): calcd. for C21H25N2OS+ [M + H+] 353.1682;
found 353.1680.
N-(3-Butyl-5-(4-chlorophenyl)thiazolidin-2-ylidene)benzamide (3a)
Yellow solid (165 mg, 86%); mp: 104− oC. 1H NMR (600 MHz, CDCl3): δ (ppm) 0.98 (t, 3H, J = 7.2 Hz), 1.38−1.44 (m, 2H), 1.65−1.70 (m, 2H), 3.65 (dd, 1H, J = 7.2, 3.6 Hz), 3.81 (t, 2H, J = 7.8 Hz), 4.00 (dd, 1H, J = 9.6,
Chapter II 2-Iminothiazolidines 1.2 Hz), 4.67 (t, 1H, J = 7.8 Hz), 7.31 (m, 4H), 7.43 (t, 2H, J = 7.2 Hz), 7.50 (t, 1H, J = 7.2 Hz), 8.28 (d, 2H, J = 7.2 Hz); 13C{1H} NMR (100 MHz, CDCl3): δ (ppm) 13.9, 20.3, 29.4, 46.1, 47.7, 57.2, 128.2, 128.9, 129.3, 129.8, 132.0, 134.1, 136.8, 138.2, 170.7, 176.0; IR (KBr): 2959, 2929, 2865, 1618, 1538, 1405, 1247, 1092 cm-1; HRMS (ESI): calcd. for C21H22ClN2OS+ [M + H+] 385.1136;
found 385.1140.
N-(3-Butyl-5-(4-fluorophenyl)thiazolidin-2-ylidene)benzamide (4a)
Creamy solid (149 mg, 81%); mp: 91− oC. 1H NMR (600 MHz, CDCl3): δ (ppm) 0.98 (t, 3H, J = 7.2 Hz), 1.40 (m, 2H), 1.67 (m, 2H), 3.65 (dd, 1H, J = 7.8, 3.6 Hz), 3.80 (t, 2H, J = 7.8 Hz), 3.99 (dd, 1H, J = 8.4, 2.4 Hz), 4.69 (t, 1H, J = 7.8 Hz), 7.01 (t, 2H, J = 8.4 Hz), 7.35 (dd, 2H, J = 8.4, 3.0 Hz), 7.42 (t, 2H, J = 7.8 Hz), 7.49 (t, 1H, J = 7.2 Hz), 8.28 (d, 2H, J = 7.2 Hz); 13C{1H} NMR (100 MHz, CDCl3): δ (ppm) 13.9, 20.2, 29.4, 46.0, 47.6, 57.4, 115.9, 116.1, 128.2, 129.2, 129.3, 129.8, 132.0, 135.35, 135.38, 136.8, 161.3, 163.8, 170.8, 176.0; IR (KBr): 2958, 2925, 2855, 1626, 1536, 1510, 1405, 1229, 1159 cm-1; HRMS (ESI): calcd. for C21H22FN2OS+ [M + H+] 369.1431; found 369.1440.
N-(3-Isopropyl-5-phenylthiazolidin-2-ylidene)benzamide (5a)
White solid (141 mg, 87%); mp: 117− oC. 1H NMR (400 MHz, CDCl3): δ (ppm) 1.21 (d, 3H, J = 6.8 Hz), 1.26 (d, 3H, J = 6.8 Hz), 3.58 (dd, 1H, J = 7.6, 3.6 Hz), 3.91 (dd, 1H, J = 8.4, 2.4 Hz), 4.59 (t, 1H, J = 8.0 Hz), 5.09 (dt, 1H, J = 6.8 Hz), 7.22−7.29 (m, 3H), 7.32−7.37 (m, 4H), 7.42 (m, 1H), 8.22 (t, 2H, J = 8.4 Hz); 13C{1H} NMR (100 MHz, CDCl3): δ (ppm) 19.7, 20.0, 46.5, 48.4, 52.1, 127.5, 128.1, 128.3, 129.1, 129.8, 131.9, 137.0, 139.5, 170.7,
Chapter II 2-Iminothiazolidines 1404, 1327, 1243, 1059 cm-1; HRMS (ESI): calcd. for C19H21N2OS+ [M + H+] 325.1369; found 325.1375.
N-(3-Isopropyl-5-phenylthiazolidin-2-ylidene)-4-methylbenzamide (5b)
White solid (142 mg, 84%); mp: 119− oC. 1H NMR (400 MHz, CDCl3): δ (ppm) 1.26 (d, 3H, J = 6.8 Hz), 1.31 (d, 3H, J = 6.8 Hz), 2.39 (s, 3H), 3.62 (dd, 1H, J = 7.6, 3.2 Hz), 3.95 (dd, 1H, J = 8.4, 2.4 Hz), 4.64 (t, 1H, J = 8.0 Hz), 5.14 (m, 1H), 7.22 (d, 2H, J = 8.0 Hz), 7.31 (m, 3H), 7.39 (d, 2H, J = 6.8 Hz), 8.19 (d, 2H, J = 8.4 Hz); 13C{1H}
NMR (100 MHz, CDCl3): δ (ppm) 19.6, 20.0, 21.8, 46.8, 48.3, 52.1, 127.5, 128.3, 128.8, 129.1, 129.8, 134.3, 139.6, 142.3, 170.4, 176.0; IR (KBr): 3028, 2974, 2924, 2854, 1621, 1522, 1461, 1408, 1328, 1170, 947 cm-1; HRMS (ESI): calcd. for C20H23N2OS+ [M + H+] 339.1526; found 339.1530.
4-Fluoro-N-(3-isopropyl-5-phenylthiazolidin-2-ylidene)benzamide (5f)
Yellow solid (152 mg, 89%); mp: 163− oC. 1H NMR (500 MHz, CDCl3): δ (ppm) 1.30 (dd, 6H, J = 8.5, 8.5 Hz), 3.66 (dd, 1H, J = 9.5, 4.5 Hz), 3.98 (dd, 1H, J = 10.0, 3.5 Hz), 4.67 (t, 1H, J = 9.5 Hz), 5.13 (dt, 1H, J = 9.0 Hz), 7.08 (t, 2H, J = 11.0 Hz), 7.29−7.41 (m, 5H), 8.30 (dd, 2H, J = 11.0, 4.5 Hz); 13C{1H} NMR (150 MHz, CDCl3): δ (ppm) 19.7, 20.1, 46.6, 48.5, 52.2, 115.0, 115.1, 127.5, 128.4, 129.1, 132.14, 132.22, 133.29, 133.31, 139.5, 164.5, 166.2, 170.8, 174.9; IR (KBr): 3028, 2974, 2924, 2854, 1621, 1522, 1461, 1408, 1328, 1170, 947 cm-1; HRMS (ESI): calcd. for C19H20FN2OS+ [M + H+] 343.1275; found 343.1280.
N-(3-Isobutyl-5-phenylthiazolidin-2-ylidene)benzamide (6a)
Yellow gummy (154 mg, 91%). 1H NMR (600 MHz, CDCl3): δ (ppm) 1.00 (t, 6H, J = 6.6 Hz), 2.15 (dt, 1H, J =
Chapter II 2-Iminothiazolidines 7.2 Hz), 3.58 (dd, 1H, J = 7.2, 6.0 Hz), 3.66−3.73 (m, 2H), 4.02 (dd, 1H, J = 8.4, 2.4 Hz), 4.73 (t, 1H, J = 7.8 Hz), 7.31 (d, 1H, J = 7.2 Hz), 7.34 (d, 2H, J = 7.8 Hz), 7.40 (s, 2H), 7.44 (d, 2H, J = 7.2 Hz), 7.50 (t, 1H, J = 7.2 Hz), 8.28 (t, 2H, J = 7.8 Hz); 13C{1H} NMR (100 MHz, CDCl3): δ (ppm) 20.39, 20.40, 27.4, 46.8, 55.2, 58.0, 127.5, 128.1, 128.2, 129.0, 129.6, 131.8, 136.9, 139.2, 171.4, 175.8; IR (KBr): 3061, 2959, 2870, 1626, 1536, 1405, 1284, 1000 cm-1; HRMS (ESI): calcd. for C20H23N2OS+ [M + H+] 339.1526; found 339.1530.
N-(3-Isobutyl-5-phenylthiazolidin-2-ylidene)-4-methylbenzamide (6b)
Yellow solid (153 mg, 87%); mp: 107− oC. 1H NMR (400 MHz, CDCl3): δ (ppm) 0.99 (dd, 6H, J = 6.8, 2.4 Hz), 2.14 (dt, 1H, J = 6.8 Hz), 2.40 (s, 3H), 3.56 (dd, 1H, J = 7.2, 6.0 Hz), 3.64−3.72 (m, 2H), 4.00 (dd, 1H, J = 8.4, 2.4 Hz), 4.72 (t, 1H, J = 8.0 Hz), 7.24 (t, 2H, J = 8.0 Hz), 7.27−7.34 (m, 3H), 7.40 (d, 2H, J = 7.2 Hz), 8.17 (d, 2H, J = 8.0 Hz); 13C{1H} NMR (100 MHz, CDCl3): δ (ppm) 20.54, 20.55, 21.8, 27.5, 47.0, 55.4, 58.2, 127.7, 128.4, 128.9, 129.1, 129.9, 134.4, 139.4, 142.4, 171.3, 176.0; IR (KBr): 2956, 2923, 2846, 1622, 1536, 1408, 1284, 1170, 1001 cm-1; HRMS (ESI): calcd. for C21H25N2OS+ [M + H+] 353.1682; found 353.1690.
4-Fluoro-N-(3-isobutyl-5-phenylthiazolidin-2-ylidene)benzamide (6f)
Yellow solid (167 mg, 94%); mp: 148− oC. 1H NMR (400 MHz, CDCl3): δ (ppm) 0.99 (dd, 6H, J = 6.8, 2.8 Hz), 2.10−2.17 (m, 1H), 3.56 (dd, 1H, J = 7.6, 6.0 Hz), 3.63−3.74 (m, 2H), 4.02 (dd, 1H, J = 8.4, 2.8 Hz), 4.73 (t, 1H, J = 8.0 Hz), 7.09 (t, 2H, J = 8.8 Hz), 7.30−7.37 (m, 3H), 7.40 (t, 2H, J = 6.8 Hz), 8.28 (dd, 2H, J = 8.8 Hz);
13C{1H} NMR (150 MHz, CDCl3): δ (ppm) 20.5, 27.4,
Chapter II 2-Iminothiazolidines 46.9, 55.3, 58.1, 115.0, 115.1, 127.6, 128.4, 129.1, 132.07, 132.13, 133.2, 133.3, 139.2, 164.5, 166.2, 171.5, 174.8; IR (KBr): 3063, 2956, 2870, 1622, 1534, 1428, 1408, 1305, 1192, 1000 cm-1; HRMS (ESI): calcd. for C20H22FN2OS+ [M + H+] 357.1431; found 357.1440.
N-(3-Cyclohexyl-5-phenylthiazolidin-2-ylidene)benzamide (7a)
Pale yellow solid (171 mg, 94%); mp: 130− oC. 1H NMR (600 MHz, CDCl3): δ (ppm) 1.13 (m, 1H), 1.43−152 (m, 4H), 1.73 (d, 1H, J = 13.2 Hz), 1.87 (m, 2H), 1.95 (dd, 2H, J = 12.0, 2.4 Hz), 3.69 (dd, 1H, J = 7.2, 3.6 Hz), 4.01 (dd, 1H, J = 7.8, 3.0 Hz), 4.65 (t, 1H, J = 7.2 Hz), 4.73 (m, 1H), 7.29 (m, 1H), 7.34 (t, 2H, J = 7.8 Hz), 7.39 (d, 2H, J
= 7.2 Hz), 7.44 (t, 2H, J = 7.2 Hz), 7.50 (t, 1H, J = 7.2 Hz), 8.28 (d, 2H, J = 8.4 Hz); 13C{1H} NMR (100 MHz, CDCl3): δ (ppm) 24.4, 24.6, 24.7, 29.0, 29.3, 45.3, 52.2, 55.7, 126.3, 127.0, 127.1, 127.9, 128.6, 130.8, 135.7, 138.6, 169.4, 174.5; IR (KBr): 2927, 2854, 1625, 1519, 1406, 1280, 1018 cm-1; HRMS (ESI): calcd. for C22H25N2OS+ [M + H+] 365.1682; found 365.1685.
N-(3-Cyclohexyl-5-phenylthiazolidin-2-ylidene)-4-methylbenzamide (7b)
Pale yellow solid (172 mg, 91%); mp: 109− oC. 1H NMR (600 MHz, CDCl3): δ (ppm) 1.11 (m, 1H), 1.40−1.48 (m, 4H), 1.71 (d, 1H, J = 7.2 Hz), 1.85 (m, 2H), 1.92 (t, 2H, J = 12.0 Hz), 2.39 (s, 3H), 3.65 (dd, 1H, J = 7.2, 4.2 Hz), 3.96 (dd, 1H, J = 8.4, 3.0 Hz), 4.60 (t, 1H, J
= 7.8 Hz), 4.69 (m, 1H), 7.22 (d, 2H, J = 7.8 Hz), 7.26 (d, 1H, J = 7.2 Hz), 7.31 (t, 2H, J = 6.6 Hz), 7.36 (d, 2H, J = 7.2 Hz), 8.18 (d, 2H, J = 7.8 Hz); 13C{1H} NMR (100 MHz, CDCl3): δ (ppm) 21.7, 25.5, 25.76, 25.83, 30.1, 30.4, 46.4, 53.1, 56.6, 127.4, 128.2, 128.8, 129.0, 129.7, 134.3, 139.8, 142.2, 170.3, 175.8; IR (KBr): 3024, 2931,
-1
Chapter II 2-Iminothiazolidines calcd. for C23H27N2OS+ [M + H+] 379.1839; found 379.1845.
N-(3-Cyclohexyl-5-phenylthiazolidin-2-ylidene)-4-fluorobenzamide (7f)
Yellow solid (185 mg, 97%); mp: 132− oC. 1H NMR (600 MHz, CDCl3): δ (ppm) 1.09−1.16 (m, 1H), 1.42−1.50 (m, 4H), 1.72 (d, 1H, J = 13.2 Hz), 1.89 (d, 4H, J = 9.6 Hz), 3.68 (dd, 1H, J = 6.6, 4.2 Hz), 3.99 (dd, 1H, J = 8.4, 2.4 Hz), 4.63 (t, 1H, J = 7.8 Hz), 4.68 (m, 1H), 7.09 (t, 2H, J = 9.0 Hz), 7.28 (d, 1H, J = 7.2 Hz), 7.32 (t, 2H, J = 7.8 Hz), 7.36 (d, 2H, J = 7.2 Hz), 8.29 (dd, 2H, J = 9.0, 3.0 Hz); 13C{1H} NMR (150 MHz, CDCl3): δ (ppm) 25.4, 25.68, 25.74, 30.0, 30.3, 46.4, 53.1, 56.7, 114.8, 115.0, 127.3, 128.2, 128.9, 131.9, 132.0, 133.19, 133.21, 139.6, 164.3, 166.0, 170.5. 174.6; IR (KBr): 2929, 2855, 1623, 1519, 1407, 1364, 1320, 1224, 1144, 1014 cm-1; HRMS (ESI): calcd. for C22H24FN2OS+ [M + H+] 383.1588; found 383.1590.
N-(3-Cyclopropyl-5-phenylthiazolidin-2-ylidene)-4-fluorobenzamide (8a)
Brown solid (143 mg, 89%); mp: 90− oC. 1H NMR (400 MHz, CDCl3): δ (ppm) 0.95 (m, 4H), 3.00 (m, 1H), 3.65 (td, 1H, J = 9.2 Hz), 3.94 (td, 1H, J = 9.2 Hz), 4.62 (t, 1H, J = 7.6 Hz), 7.24−7.36 (m, 5H), 7.42 (t, 2H, J = 7.2 Hz), 7.49 (dd, 1H, J = 8.4, 1.6 Hz), 8.32 (d, 2H, J = 7.2 Hz);
13C{1H} NMR (100 MHz, CDCl3): δ (ppm) 6.8, 7.1, 29.9, 46.7, 57.8, 127.5, 128.1, 128.3, 129.0, 129.8, 132.1, 136.7, 139.1, 172.6, 176.1; IR (KBr): 3062, 2924, 2853, 1627, 1521, 1402, 1329, 1220, 1024 cm-1; HRMS (ESI): calcd.
for C19H19N2OS+ [M + H+] 323.1213; found 323.1215.
N-(3-Cyclopropyl-5-phenylthiazolidin-2-ylidene)-4-methylbenzamide (8b)
Yellow solid (144 mg, 86%); mp: 117− oC. 1H NMR (400 MHz, CDCl3): δ (ppm) 0.87−0.99 (m, 4H), 2.38 (s,
Chapter II 2-Iminothiazolidines 3H), 2.98 (m, 1H), 3.63 (dd, 1H, J = 8.0, 3.2 Hz), 3.92 (dd, 1H, J = 8.0, 2.8 Hz), 4.61 (t, 1H, J = 7.6 Hz), 7.22 (t, 3H, J = 8.0 Hz), 7.33 (m, 4H), 8.20 (d, 2H, J = 8.0 Hz);
13C{1H} NMR (100 MHz, CDCl3): δ (ppm) 6.8, 7.2, 21.8, 29.9, 46.6, 57.8, 127.5, 128.3, 128.9, 129.0, 130.0, 134.1, 139.2, 142.5, 172.3, 176.1; IR (KBr): 3027, 2923, 2853, 1622, 1523, 1401, 1330, 1169, 1019 cm-1; HRMS (ESI):
calcd. for C20H21N2OS+ [M + H+] 337.1369; found 337.1365.
N-(3-Cyclopropyl-5-phenylthiazolidin-2-ylidene)-4-fluorobenzamide (8f)
Yellow solid (158 mg, 93%); mp: 122− oC. 1H NMR (400 MHz, CDCl3): δ (ppm) 0.90− (m, 4H), 2.97−3.03 (m, 1H), 3.68 (dd, 1H, J = 7.6, 3.2 Hz), 3.97 (dd, 1H, J = 8.0, 2.8 Hz), 4.65 (t, 1H, J = 8.0 Hz), 7.09 (dd, 3H, J = 8.8, 2.0 Hz), 7.31−7.36 (m, 4H), 8.33 (dd, 2H, J = 9.2, 3.2 Hz);
13C{1H} NMR (100 MHz, CDCl3): δ (ppm) 6.8, 7.2, 30.0, 46.7, 57.9, 115.0, 115.2, 127.5, 128.4, 129.1, 132.2, 132.3, 133.10, 133.13, 139.0, 164.2, 166.7, 172.8, 175.0; IR (KBr): 3002, 2923, 2848, 1623, 1523, 1409, 1331, 1223, 1146, 1028 cm-1; HRMS (ESI): calcd. for C19H18FN2OS+ [M + H+] 341.1118; found 341.1120.
N-(3-(Adamantan-1-yl)-5-phenylthiazolidin-2-ylidene)benzamide (9a)
Creamy solid (198 mg, 95%); mp: 160− oC. 1H NMR (400 MHz, CDCl3): δ (ppm) 1.77 (q, 6H, J = 12.4 Hz), 2.20 (s, 3H), 2.47 (t, 6H, J = 14.4 Hz), 3.83 (dd, 1H, J = 7.6, 3.2 Hz), 4.15 (dd, 1H, J = 7.6, 3.2 Hz), 4.53 (t, 1H, J
= 8.0 Hz), 7.26−7.36 (m, 3H), 7.41−7.52 (m, 5H), 8.29 (dd, 2H, J = 8.8, 1.6 Hz); 13C{1H} NMR (100 MHz, CDCl3): δ (ppm) 30.1, 36.4, 39.8, 45.4, 54.9, 60.9, 127.4, 128.05, 128.10, 128.9, 129.5, 131.7, 137.3, 139.6, 170.2, 174.8; IR (KBr): 3067, 2908, 2851, 1625, 1506, 1451,
Chapter II 2-Iminothiazolidines 1387, 1227, 1156, 1054 cm-1; HRMS (ESI): calcd. for C26H29N2OS+ [M + H+] 417.1995; found 417.1202.
N-(3-(Adamantan-1-yl)-5-phenylthiazolidin-2-ylidene)-4-methylbenzamide (9b) Yellow solid (196 mg, 91%); mp: 123− oC. 1H NMR (600 MHz, CDCl3): δ (ppm) 1.75 (q, 6H, J = 12.0 Hz), 2.18 (s, 3H), 2.39 (s, 3H), 2.45 (q, 6H, J = 12.0 Hz), 3.80 (dd, 1H, J = 7.8, 3.0 Hz), 4.12 (dd, 1H, J = 7.8, 3.0 Hz), 4.51 (t, 1H, J = 7.8 Hz), 7.26 (dd, 3H, J = 7.8, 7.2 Hz), 7.32 (t, 2H, J = 7.8 Hz), 7.40 (d, 2H, J = 7.8 Hz), 8.16 (d, 2H, J = 8.4 Hz); 13C{1H} NMR (150 MHz, CDCl3): δ (ppm) 21.7, 30.1, 36.4, 39.9, 45.5, 54.9, 60.9, 127.4, 127.6, 128.1, 128.9, 129.3, 129.6, 134.6, 139.6., 170.0, 174.9; IR (KBr): 2909, 2852, 1649, 1497, 1384, 1225, 1050, 1019 cm-1; HRMS (ESI): calcd. for C27H31N2OS+ [M + H+] 431.2152; found 431.2160.
N-(3-(Adamantan-1-yl)-5-phenylthiazolidin-2-ylidene)-4-fluorobenzamide (9f)
Yellow solid (212 mg, 98%); mp: 146− oC. 1H NMR (600 MHz, CDCl3): δ (ppm) 1.76 (m, 6H), 2.20 (s, 3H), 2.46 (q, 6H, J = 11.4 Hz), 3.84 (dd, 1H, J = 7.2, 3.6 Hz), 4.15 (dd, 1H, J = 7.8, 3.0 Hz), 4.54 (t, 1H, J = 7.2 Hz), 7.10 (m, 2H), 7.30 (dd, 1H, J = 7.2, 4.2 Hz), 7.34 (m, 2H), 7.41 (t, 2H, J = 7.2 Hz), 8.27 (dd, 2H, J = 9.0, 3.0 Hz);
13C{1H} NMR (100 MHz, CDCl3): δ (ppm) 30.1, 36.4, 39.9, 45.5, 55.0, 61.1, 115.01, 115.2, 127.4, 128.2, 129.0, 131.8, 131.9, 133.58, 133.61, 139.5, 164.3, 166.0, 170.4, 173.9; IR (KBr): 2920, 2853, 1624, 1510, 1385, 1226, 1018 cm-1; HRMS (ESI): calcd. for C26H28FN2OS+ [M + H+] 435.1901; found 435.1906.
N-(3-Benzyl-5-phenylthiazolidin-2-ylidene)benzamide (10a)
Pale yellow solid (154 mg, 83%); mp: 94− oC. 1H NMR (600 MHz, CDCl3): δ (ppm) 3.63 (dd, 1H, J = 7.8, 3.6 Hz),
Chapter II 2-Iminothiazolidines 3.92 (dd, 1H, J = 8.4, 3.6 Hz), 4.72 (t, 1H, J = 8.4 Hz), 5.07 (dd, 2H, J = 14.4, 13.8 Hz), 7.32 (m, 5H), 7.39 (m, 5H), 7.47 (t, 2H, J = 7.8 Hz), 7.54 (t, 1H, J = 7.2 Hz), 8.38 (d, 2H, J = 7.2 Hz); 13C{1H} NMR (100 MHz, CDCl3): δ (ppm) 46.7, 51.4, 56.5, 127.6, 128.2, 128.26, 128.32, 128.6, 129.05, 129.07, 129.9, 132.1, 135.8, 136.8, 139.2, 171.6, 176.1; IR (KBr): 3062, 2623, 2853, 1626, 1533, 1403, 1325, 1248, 1161 cm-1; HRMS (ESI): calcd. for C23H21N2OS+ [M + H+] 373.1369; found 373.1362.
5-Ethyl 2-(benzoylimino)-3-(1-phenylethyl)thiazolidine-5-carboxylate (11a)
Yellow gummy (176 mg, 92%). 1H NMR (400 MHz, CDCl3): δ (ppm) 1.26 (t, 3H, J = 6.8 Hz), 1.75 (d, 3H, J = 7.2 Hz), 3.27 (m, 1H), 3.98 (m, 2H), 4.18 (q, 2H, J = 7.2 Hz), 6.33 (q, 1H, J = 6.8 Hz), 7.31 (d, 1H, J = 6.8 Hz), 7.38 (m, 4H), 7.44 (d, 2H, J = 7.6 Hz), 7.49 (d, 1H, J = 7.2 Hz), 8.32 (t, 2H, J = 7.2 Hz); 13C{1H} NMR (150 MHz, CDCl3): δ (ppm) 14.1, 15.7, 42.2, 45.9, 54.5, 62.2, 127.4, 128.1, 128.2, 128.9, 129.8, 132.1, 136.3, 138.7, 169.4, 170.5, 176.0; IR (KBr): 2980, 2931, 1734, 1616, 1405, 1326, 1256, 1199, 1021 cm-1; HRMS (ESI): calcd. for C21H23N2O3S+ [M + H+] 383.1424; found 383.1430.
5-Ethyl 2-((4-methylbenzoyl)imino)-3-(1-phenylethyl)thiazolidine-5-carboxylate (11b)
Yellow gummy (176 mg, 89%). 1H NMR (600 MHz, CDCl3): δ (ppm) 1.26 (t, 3H, J = 7.2 Hz), 1.74 (d, 3H, J = 7.2 Hz), 2.39 (s, 3H), 3.25 (dd, 1H, J = 7.2, 6.6 Hz), 3.97 (m, 2H), 4.18 (m, 2H), 6.32 (q, 1H, J = 7.2 Hz), 7.22 (d, 2H, J = 7.8 Hz), 7.29 (t, 1H, J = 7.2 Hz), 7.35 (d, 2H, J = 7.8 Hz), 7.38 (d, 2H, J = 7.2 Hz), 8.20 (d, 2H, J = 7.2 Hz);
13C{1H} NMR (150 MHz, CDCl3): δ (ppm) 14.1, 15.7, 21.7, 42.2, 45.8, 54.4, 62.2, 127.4, 128.1, 128.9, 129.9, 133.7, 138.8, 142.6, 169.2, 170.5, 176.0; IR (KBr): 2980,
Chapter II 2-Iminothiazolidines 2927, 1734, 1613, 1529, 1407, 1324, 1199, 1019 cm-1; HRMS (ESI): calcd. for C22H25N2O3S+ [M + H+] 397.1580; found 397.1584.
5-Ethyl 2-((4-chlorobenzoyl)imino)-3-(1-phenylethyl)thiazolidine-5-carboxylate (11e) Yellow gummy (197 mg, 95%). 1H NMR (400 MHz, CDCl3): δ (ppm) 1.28 (t, 3H, J = 7.6 Hz), 1.75 (d, 3H, J = 7.2 Hz), 3.29 (m, 1H), 3.97−4.02 (m, 2H), 4.20 (q, 2H, J
= 7.2 Hz), 6.29 (q, 1H, J = 6.8 Hz), 7.36 (m, 7H), 8.23 (d, 2H, J = 8.8 Hz); 13C{1H} NMR (150 MHz, CDCl3): δ (ppm) 14.2, 15.8, 42.3, 46.1, 54.6, 62.4, 127.4, 128.3, 128.4, 129.0, 131.3, 135.0, 138.3, 138.7, 169.8, 170.5, 175.2; IR (KBr): 3063, 2980, 2934, 1735, 1617, 1528, 1405, 1325, 1198, 1013 cm-1; HRMS (ESI): calcd. for C21H22ClN2O3S+ [M + H+] 417.1034; found 417.1040.
N-(3-Butyl-5-(p-tolyl)thiazolidin-2-ylidene)cyclohexanecarboxamide (2k)
Colorless gummy (134 mg, 74%). 1H NMR (400 MHz, CDCl3): δ (ppm) 0.96 (t, 3H, J = 7.2 Hz), 1.28 (m, 7H), 1.61 (m, 3H), 1.76 (m, 2H), 1.96 (d, 2H, J = 12.6), 2.33 (s, 3H), 2.38 (m, 1H), 3.60 (dd, 1H, J = 8.4, 2.8 Hz), 3.67 (td, 2H, J = 7.2 Hz), 3.88 (dd, 1H, J = 8.0, 1.2 Hz), 4.62 (t, 1H, J = 8.0 Hz), 7.14 (d, 2H, J = 8.0 Hz), 7.25 (d, 2H, J = 8.0 Hz); 13C{1H} NMR (100 MHz, CDCl3): δ (ppm) 14.0, 20.2, 21.3, 26.1, 26.2, 29.4, 29.8, 29.9, 46.7, 47.3, 48.2, 57.2, 127.6, 129.8, 136.3, 138.1, 170.1, 188.0; IR (KBr):
2929, 2856, 1735, 1634, 1526, 1449, 1165, 1128 cm-1; HRMS (ESI): calcd. for C21H31N2OS+ [M + H+] 359.2152;
found 359.2150.
N-(3-Butyl-5-(4-fluorophenyl)thiazolidin-2-ylidene)cyclohexanecarboxamide (4k) Colorless gummy (121 mg, 67%). 1H NMR (400 MHz, CDCl3): δ (ppm) 0.95 (t, 3H, J = 7.2 Hz), 1.29 (m, 7H), 1.61 (m, 3H), 1.76 (m, 2H), 1.95 (m, 2H), 2.37 (m, 1H),
Chapter II 2-Iminothiazolidines 3.56 (dd, 1H, J = 7.6, 3.6 Hz), 3.66 (t, 2H, J = 7.2 Hz), 3.89 (dd, 1H, J = 8.4, 2.4 Hz), 4.61 (t, 1H, J = 8.0 Hz), 7.01 (t, 2H, J = 8.4 Hz), 7.33 (dd, 2H, J = 5.6, 3.2 Hz);
13C{1H} NMR (100 MHz, CDCl3): δ (ppm) 13.9, 20.1, 26.07, 26.11, 26.3, 29.3, 29.7, 29.8, 46.1, 47.3, 48.2, 57.2, 115.9, 116.1, 129.25, 129.33, 135.37, 135.41, 161.3, 163.8, 169.7, 188.0; IR (KBr): 2929, 2856, 1734, 1626, 1535, 1453, 1230, 1163, 1017 cm-1; HRMS (ESI): calcd.
for C20H28FN2OS+ [M + H+] 363.1901; found 363.1905.
N-(5-Phenyl-3-tosylthiazolidin-2-ylidene)benzamide (12a)
Yellow solid (37 mg, 17%); mp: 115− oC. 1H NMR (400 MHz, CDCl3): δ (ppm) 2.40 (s, 3H), 4.16 (dd, 1H, J
= 8.8, 2.0 Hz), 4.65 (dd, 1H, J = 7.2, 3.2 Hz), 4.79 (dd, 1H, J = 7.2, 1.2 Hz), 7.27 (d, 2H, J = 8.0 Hz), 7.37 (m, 5H), 7.49 (m, 3H), 7.97 (dd, 2H, J = 6.8, 4.8 Hz), 8.27 (dd, 2H, J = 8.4, 1.6 Hz); 13C{1H} NMR (150 MHz, CDCl3): δ (ppm) 21.9, 46.8, 55.8, 127.8, 128.7, 128.8, 129.0, 129.4, 129.8, 130.5, 133.3, 134.7, 135.3, 136.8, 145.8, 168.0, 176.0; IR (KBr): 2923, 2854, 1640, 1561, 1451, 1170, 1087 cm-1; HRMS (ESI): calcd. for C23H21N2O3S2+ [M + H+] 437.0988; found 437.0990.
Chapter II 2-Iminothiazolidines