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W. Yi et al. / European Journal of Medicinal Chemistry 46 (2011) 4330e4335
(ESI) 198 (M þ H)þ, 220 (M þ Na)þ; Anal. Calcd for C8H8FN3S: C,
8.07 (br s, 1H, NH2), 7.80 (s, 1H, ArH), 7.44 (br s, 1H, NH2), 7.42 (d,
48.72; H, 4.09, N, 21.31; found: C, 48.61; H, 4.19; N, 21.66.
J ¼ 8.0 Hz,1H, ArH), 7.20 (t, J ¼ 7.6 Hz,1H, ArH), 7.13 (t, J ¼ 7.6 Hz,1H,
ArH); 13C NMR (DMSO-d6)
d: 178.5, 142.9, 139.1, 133.1, 125.9, 124.7,
4.1.5. 1-[(4-Fluorophenyl)methylene]thiosemicarbazone (1d)
124.2, 122.7, 113.8, 113.2; MS (ESI) 219 (M þ H)þ, 241 (M þ Na)þ.
Yield 85%; m.p. 197e198 ꢀC; 1H NMR (DMSO-d6)
d: 11.45 (s, 1H,
NH), 8.22 (br s, 1H, NH2), 8.05 (br s, 1H, NH2), 8.03 (s, 1H, CH), 7.87
4.1.13. 1-[(1-Methyl-indol-3-yl)methylene]thiosemicarbazone (1l)
(m, 2H, ArH), 7.23 (t, J ¼ 8.8 Hz, 2H, ArH); 13C NMR (DMSO-d6)
d:
Yield 89%; m.p. 206e207 ꢀC; 1H NMR (400 MHz, DMSO-d6)
d:
180.0, 166.2, 163.8, 143.0, 132.9, 132.8, 131.6, 131.5, 117.8, 117.6; MS
(ESI) 198 (M þ H)þ, 220 (M þ Na)þ; Anal. Calcd for C8H8FN3S: C,
48.72; H, 4.09, N, 21.31; found: C, 48.99; H, 4.11; N, 21.47.
11.18 (s, 1H, NH), 8.28 (s, 1H, CH), 8.25 (d, J ¼ 8.0 Hz, 1H, ArH),
8.07 (br s, 1H, NH2), 7.79 (s, 1H, ArH), 7.48 (d, J ¼ 8.0 Hz, 1H, ArH),
7.46 (br s, 1H, NH2), 7.26 (m, 1H, ArH), 7.17 (m, 1H, ArH), 3.80 (s,
3H, CH3); 13C NMR (DMSO-d6)
d: 178.4, 142.4, 139.6, 136.7, 126.3,
4.1.6. 1-(Furan-2-ylmethylene)thiosemicarbazone (1e)
124.7, 124.4, 122.9, 112.1, 34.8; MS (ESI) 233 (M þ H)þ, 255
Yield 87%; m.p. 153e154 ꢀC; 1H NMR (DMSO-d6)
d: 11.44 (s, 1H,
(M þ Na)þ.
NH), 8.23 (br s, 1H, NH2), 7.96 (s, 1H, CH), 7.80 (s, 1H, ArH), 7.64 (br s,
1H, NH2), 6.96 (d, J ¼ 2.8 Hz, 1H, ArH), 6.61 (s, 1H, ArH); 13C NMR
4.1.14. 1-[(1-Methyl-1H-indol-3-yl)methylene]thiosemicarbazone
(DMSO-d6)
d
: 179.7, 151.4, 147.0, 134.5, 114.8, 114.3; MS (ESI) 170
(1m)
(M þ H)þ, 192 (M þ Na)þ; Anal. Calcd for C6H7N3OS: C, 42.59; H,
Yield 78%; m.p. 211e212 ꢀC; 1H NMR (DMSO-d6)
d: 11.50 (s, 1H,
4.17, N, 24.83; found: C, 42.53; H, 4.49; N, 24.68.
NH), 11.03 (s, 1H, NH), 8.42 (s, 1H, CH), 8.20 (br s, 1H, NH2), 8.13 (d,
J ¼ 7.8 Hz, 1H, ArH), 8.04 (s, 1H, ArH), 8.02 (br s, 1H, NH2), 7.86 (d,
J ¼ 8.4 Hz, 1H, ArH), 7.81 (d, J ¼ 8.4 Hz, 1H, ArH), 7.19 (dd, J ¼ 8.4 and
4.1.7. 1-[(1H-Pyrrol-2-yl)methylene]thiosemicarbazone (1f)
Yield 77%; m.p. 200e201 ꢀC; 1H NMR (DMSO-d6)
d
: 11.35 (s, 1H,
1.6 Hz, 1H, ArH), 3.89 (s, 3H, CH3); 13C NMR (DMSO-d6)
d: 178.1,
NH), 11.27 (s, 1H, NH), 8.08 (br s, 1H, NH2), 7.98 (br s, 1H, NH2), 7.82
142.8, 142.7, 137.7, 127.0, 123.8, 123.4, 122.5, 112.8, 108.9, 13.5; MS
(s, 1H, CH), 6.97 (d, J ¼ 1.2 Hz, 1H, ArH), 6.30 (m, 1H, ArH), 6.10 (dd,
(ESI) 233 (M þ H)þ, 255 (M þ Na)þ.
J ¼ 8.4 and 3.6 Hz, 1H, ArH); 13C NMR (DMSO-d6)
d: 179.2, 135.7,
129.6, 123.8, 114.9, 111.2; MS (ESI) 169 (M þ H)þ, 191 (M þ Na)þ;
Anal. Calcd for C6H8N4S: C, 42.84; H, 4.80, N, 33.31; found: C, 42.73;
H, 5.14; N, 33.24.
4.1.15. 1-[(1H-Indol-2-yl)methylene]thiosemicarbazone (1n)
Yield 72%; m.p. 231e231 ꢀC; 1H NMR (DMSO-d6)
d: 11.59 (s, 1H,
NH), 11.42 (s, 1H, NH), 8.34 (br s, 1H, NH2), 8.19 (br s, 1H, NH2),
8.01(s, 1H, CH), 7.55 (d, J ¼ 8.0 Hz, 1H, ArH), 7.36 (d, J ¼ 8.0 Hz, 1H,
ArH), 7.17 (t, J ¼ 8.0 Hz, 1H, ArH), 7.01 (t, J ¼ 8.0 Hz, 1H, ArH), 6.77 (s,
4.1.8. 1-(Pyridin-2-ylmethylene)thiosemicarbazone (1g)
Yield 81%; m.p. 215e216 ꢀC; 1H NMR (DMSO-d6)
d: 11.65 (s, 1H,
1H, ArH); 13C NMR (DMSO-d6)
d: 179.9, 139.1, 135.8, 135.2, 130.0,
NH), 8.55(d, J ¼ 8.4 Hz,1H, ArH), 8.36(br s,1H, NH2), 8.28(d, J ¼ 8.4 Hz,
125.5, 122.9, 121.5, 113.1, 108.1; MS (ESI) 219 (M þ H)þ, 241
1H, ArH), 8.18 (br s, 1H, NH2), 8.08 (s, 1H, CH), 7.82 (t, J ¼ 8.4 Hz, 1H,
(M þ Na)þ.
ArH), 7.36 (t, J ¼ 8.4 Hz,1H, ArH); 13C NMR (DMSO-d6)
d: 180.4,155.3,
151.3, 144.5, 138.5, 126.1, 122.2; MS (ESI) 203 (M þ Na)þ.
4.1.16. 1-[(1-Methyl-indol-2-yl)methylene]thiosemicarbazone (1o)
Yield 92%; m.p. 204e205 ꢀC; 1H NMR (DMSO-d6)
d: 11.44 (s, 1H,
4.1.9. 1-(Quinolin-2-ylmethylene)thiosemicarbazone (1h)
NH), 8.28 (br s, 1H, NH2), 8.25 (s, 1H, CH), 7.66 (br s, 1H, NH2), 7.56
Yield 88%; m.p. 242e243 ꢀC; 1H NMR (DMSO-d6)
d: 11.83 (s, 1H,
(d, J ¼ 8.0 Hz, 1H, ArH), 7.50 (d, J ¼ 8.0 Hz, 1H, ArH), 7.23e7.21 (m,
NH), 8.47 (br s, 1H, NH2), 8.44 (d, J ¼ 8.8 Hz, 1H, ArH), 8.35 (br s, 1H,
NH2), 8.44 (d, J ¼ 7.6 Hz,1H, ArH), 8.24 (s,1H, CH), 7.99 (m, 2H, ArH),
7.76 (t, J ¼ 7.6 Hz, 1H, ArH), 7.59 (d, J ¼ 7.6 Hz, 1H, ArH); 13C NMR
1H, ArH), 6.94 (s, 1H, ArH), 3.96 (s, 3H, CH3); 13C NMR (DMSO-d6)
d:
179.6, 141.2, 138.1, 135.3, 128.8, 125.3, 122.9, 121.9, 112.1, 109.0, 33.8;
MS (ESI) 233 (M þ H)þ, 255 (M þ Na)þ.
(DMSO-d6) d: 180.5, 155.9, 149.3, 144.6, 138.3, 132.0, 130.8, 129.9,
129.8, 129.2, 120.1; MS (ESI) 231(M þ H)þ, 253 (M þ Na)þ.
4.1.17. 1-[(1H-Indol-5-yl)methylene]thiosemicarbazone (1p)
Yield 76%; m.p. 217e218 ꢀC; 1H NMR (DMSO-d6)
d: 11.28 (s, 2H,
4.1.10. 1-(Naphthalen-2-ylmethylene)thiosemicarbazone (1i)
NH), 8.14 (s, 1H, CH), 8.08 (br s, 1H, NH2), 7.88 (br s, 1H, NH2), 7.86 (s,
Yield 82%; m.p. 245e246 ꢀC; 1H NMR (DMSO-d6)
d
: 11.57 (s, 1H,
1H, ArH), 7.66 (d, J ¼ 8.4 Hz, 1H, ArH), 7.41 (d, J ¼ 8.4 Hz, 1H, ArH),
NH), 8.30 (br s, 1H, NH2), 8.23 (s, 1H, CH), 8.19 (d, J ¼ 8.4 Hz, 1H,
7.40 (s, 1H, ArH), 6.46 (s, 1H, ArH); 13C NMR (DMSO-d6)
d: 179.3,
ArH), 8.13 (br s, 1H, NH2), 8.11 (s, 1H, ArH), 8.00e7.85 (m, 3H, ArH),
146.6, 138.9, 129.6, 128.4, 127.3, 123.1, 121.9, 113.8, 103.9; MS (ESI)
7.54e7.52 (m, 2H, ArH); 13C NMR (DMSO-d6)
d
: 179.9, 144.3, 135.6,
219 (M þ H)þ, 241 (M þ Na)þ.
134.8, 134.0, 130.9, 130.2, 129.7, 129.0, 128.7, 125.1; MS (ESI) 230
(M þ H)þ, 252 (M þ Na)þ.
4.1.18. 1-[(1-Methyl-indol-5-yl)methylene]thiosemicarbazone (1q)
Yield 90%; m.p. 215e216 ꢀC; 1H NMR (DMSO-d6)
d: 11.31 (s, 1H,
4.1.11. 1-(Naphthalen-1-ylmethylene)thiosemicarbazone (1j)
NH), 8.15 (s, 1H, CH), 8.11 (br s, 1H, NH2), 7.92 (br s, 1H, NH2), 7.87 (s,
1H, ArH), 7.73 (d, J ¼ 8.4 Hz, 1H, ArH), 7.46 (d, J ¼ 8.4 Hz, 1H, ArH),
7.36 (d, J ¼ 3.2 Hz, 1H, ArH), 6.47 (d, J ¼ 3.2 Hz, 1H, ArH), 3.82 (s, 3H,
Yield 87%; m.p. 233e234 ꢀC; 1H NMR (DMSO-d6)
d: 11.49 (s, 1H,
NH), 8.92 (s, 1H, CH), 8.35 (d, J ¼ 8.4 Hz, 1H, ArH), 8.33 (s, 1H, NH2),
8.23 (d, J ¼ 7.9 Hz, 1H, ArH), 8.21 (s, 1H, NH2), 7.99 (d, J ¼ 8.4 Hz, 2H,
ArH), 7.65 (dd, J1 ¼ J2 ¼ 7.9 Hz,1H, ArH), 7.59e7.54 (d, J ¼ 8.4 Hz, 2H,
CH3); 13C NMR (DMSO-d6)
d: 179.4, 146.4, 139.3, 132.7, 129.9, 127.3,
123.3, 121.9, 112.2, 103.2, 34.7; MS (ESI) 233 (M þ H)þ, 255
ArH); 13C NMR (DMSO-d6)
d: 179.9, 143.0, 135.4, 132.5, 132.3, 131.3,
(M þ Na)þ.
130.9, 129.3, 128.2, 127.8, 127.6, 124.9; MS (ESI) 230 (M þ H)þ, 252
(M þ Na)þ; Anal. Calcd for C12H11N3S: C, 62.86; H, 4.84, N, 18.33;
found: C, 62.96; H, 5.00; N, 18.51. This compound was previously
reported in Ref. [23].
4.1.19. 1-(2-Phenylethylidene)thiosemicarbazone (1r)
Yield 81%; m.p. 163e164 ꢀC; 1H NMR (DMSO-d6)
d: 11.17 (s, 1H,
NH), 8.07 (br s, 1H, NH2), 7.59 (br s, 1H, NH2), 7.47 (s, 1H, CH), 7.33
(m, 2H, ArH), 7.28 (m, 3H, ArH), 3.52 (s, 2H, CH2); 13C NMR (DMSO-
4.1.12. 1-[(1H-Indol-3-yl)methylene]thiosemicarbazone (1k)
d6) d: 179.8, 147.5, 138.7, 130.9, 130.7, 128.7, 40.1; MS (ESI) 194
Yield 68%; m.p. 230e231 ꢀC; 1H NMR (DMSO-d6)
d: 11.61 (s, 1H,
(M þ H)þ, 216 (M þ Na)þ; Anal. Calcd for C9H11N3S: C, 55.94; H,
NH), 11.20 (s, 1H, NH), 8.31 (s, 1H, CH), 8.23 (d, J ¼ 8.0 Hz, 1H, ArH),
5.74, N, 21.75; found: C, 55.49; H, 5.82; N, 21.40.