2704 J ournal of Medicinal Chemistry, 2002, Vol. 45, No. 13
Du et al.
Da ta for 2-Meth oxy-1-n a p h th a ld eh yd e Th io Sem ica r -
ba zon e (1n ): mp 156.2-157.6 °C; 1H NMR δ 3.96 (s, 3H), 7.40
(t, 1H, J ) 7.4), 7.48 (d, 1H, J ) 9.2), 7.50 (br s, 1H), 7.56 (t,
1H, J ) 7.8), 7.88 (d, 1H, J ) 8.0), 8.02 (d, 1H, J ) 9.2), 8.20
(br s, 1H), 8.80 (s, 1H), 8.92 (d, 1H, J ) 8.8), 11.48 (s, 1H);
HRMS (EI) m/z (M+) calcd for C13H13N3OS 259.0779, found
259.0772.
Da ta for 3′-Ch lor op r op iop h en on e Th io Sem ica r ba -
zon e (2a ): mp 136.6-138.3 °C; IR (neat, cm-1) 3408, 3203,
3155, 2970, 2941, 1598, 1511, 1472, 1418, 1301, 1233, 1112,
1053, 1004, 859, 791; 1H NMR δ 0.98 (t, 3H, J ) 7.4), 2.86 (q,
2H, J ) 7.6), 7.41 (m, 2H), 7.82 (m, 1H), 8.03 (s, 1H), 8.08 (br
s, 1H), 8.31 (br s, 1H), 10.36 (s, 1H); HRMS (EI) m/z (M+) calcd
for C10H12ClN3S 241.0440, found 241.0449.
J ) 2.8, 8.0), 7.44 (m, 2H), 7.88 (br s, 1H), 8.21 (br s, 1H),
10.12 (s, 1H); HRMS (EI) m/z (M+) calcd for C10H13N3OS
223.0779, found 223.0777.
Da ta for 2′-Br om oa cetop h en on e Th io Sem ica r ba zon e
1
(2l): yield 40%; mp 144.5-146.2 °C; H NMR δ 2.27 (s, 3H),
7.31 (m, 1H), 7.42 (m, 2H), 7.60 (br s, 1H), 7.65 (d, 1H, J )
8.0), 8.24 (br s, 1H), 10.34 (s, 1H); HRMS (EI) m/z (M+) calcd
for C9H10BrN3S 270.9779, found 270.9775.
Da ta for 2′-Ch lor oa cetop h en on e Th io Sem ica r ba zon e
(2m ): yield 45%; mp 155.8-156.7 °C; 1H NMR δ 2.28 (s, 3H),
7.38 (m, 2H), 7.49 (m, 2H), 7.62 (br s, 1H), 8.24 (br s, 1H),
10.34 (s, 1H); HRMS (EI) m/z (M+) calcd for C9H10ClN3S
227.0284, found 227.0289.
Da ta for 2,3-Dich lor oben za ld eh yd e Th io Sem ica r ba -
Da ta for 3′-Tr iflu or om eth ylp r op iop h en on e Th io Sem i-
ca r ba zon e (2b): mp 156.0-157.9 °C; IR (neat, cm-1) 3427,
3272, 3155, 3053, 2975, 2941, 1618, 1525, 1481, 1345, 1306,
1
zon e (2n ): mp 232.3-233.6 °C; H NMR δ 7.37 (t, 1H, J )
8.0), 7.65 (m, 1H), 8.17 (br s, 1H), 8.29 (d, 1H, J ) 8.0), 8.35
(br s, 1H), 8.48 (s, 1H), 11.67 (s, 1H); HRMS (EI) m/z (M+)
calcd for C8H7Cl2N3S 246.9738, found 246.9730.
1
1189, 1146, 1078, 864, 810, 703; H NMR δ 1.00 (t, 3H, J )
7.4), 2.92 (q, 2H, J ) 7.4), 7.61 (t, 1H, J ) 7.8), 7.72 (d, 1H, J
) 7.6), 8.11 (br s, 1H), 8.20 (s, 2H), 8.35 (br s, 1H), 10.42 (s,
1H); HRMS (EI) m/z (M+) calcd for C11H12F3N3S 275.0704,
found 275.0709. Anal. (C11H12F3N3S) C, H, F, N, S.
Da ta for 3,5-Dich lor oben za ld eh yd e Th io Sem ica r ba -
1
zon e (2o): mp 234.1-235.5 °C; H NMR δ 7.57 (t, 1H, J )
1.6), 7.93 (d, 2H, J ) 1.6), 7.96 (s, 1H), 8.31 (br s, 1H), 11.59
(s, 1H); HRMS (EI) m/z (M+) calcd for C8H7Cl2N3S 246.9738,
found 246.9737.
Da ta for 3′-F lu or op r op iop h en on e Th io Sem ica r ba -
1
zon e (2c): mp 138.8-139.5 °C; H NMR δ 0.99 (t, 3H, J )
Da ta for 2-Tr iflu or om eth ylben za ld eh yd e Th io Sem i-
ca r ba zon e (2p ): mp 248.3-249.4 °C; 1H NMR δ 7.58 (t, 1H,
J ) 7.6), 7.68 (t, 1H, J ) 7.6), 7.75 (d, 1H, J ) 8.0), 8.15 (br s,
1H), 8.35 (br s, 1H), 8.43 (s, 1H), 8.50 (d, 1H, J ) 8.0), 11.67
(s, 1H); HRMS (EI) m/z (M+) calcd for C9H8F3N3S 247.0391,
found 247.0391.
7.6), 2.86 (q, 2H, J ) 7.6), 7.20 (dt, 1H, J ) 2.4, 8.6), 7.43 (m,
1H), 7.69 (d, 1H, J ) 8.0), 7.87 (d, 1H, J ) 11.2), 8.07 (br s,
1H), 8.31 (br s, 1H), 10.36 (s, 1H); HRMS (EI) m/z (M+) calcd
for C10H12FN3S 225.0736, found 225.0738.
Da t a for P r op iop h en on e Th io Sem ica r b a zon e (2d ):
mp 116.8-117.9; 1H NMR δ 1.01 (t, 3H, J ) 7.6), 2.86 (q, 2H,
J ) 7.6), 7.38 (m, 3H), 7.89 (m, 3H), 8.22 (br s, 1H), 10.27 (s,
1H); HRMS (EI) m/z (M+) calcd for C10H13N3S 207.0830, found
207.0826.
Da ta for 3-Br om oben za ld eh yd e Th io Sem ica r ba zon e
(3a ): mp 200.6-210.9 °C; IR (neat, cm-1) 3388, 3233, 3149,
3024, 2984, 2805, 1604, 1534, 1467, 1355, 1310, 1220, 1101,
1
941, 897, 832, 792; H NMR δ 7.34 (t, 1H, J ) 7.6), 7.55 (d,
Da ta for 4′-Br om op r op iop h en on e Th io Sem ica r ba -
1H, J ) 7.2), 7.68 (d, 1H, J ) 7.6), 7.99 (s, 1H), 8.18 (s, 2H),
8.24 (br s, 1H), 11.49 (s, 1H); HRMS (EI) m/z (M+) calcd for
C8H8BrN3S 256.9622, found 256.9618.
1
zon e (2e): mp 171.3-173.0 °C; H NMR δ 0.98 (t, 3H, J )
7.4), 2.84 (q, 2H, J ) 7.4), 7.55 (d, 2H, J ) 8.4), 7.88 (d, 2H,
8.4), 7.97 (br s, 1H), 8.31 (br s, 1H), 10.38 (s, 1H); HRMS (EI)
m/z (M+) calcd for C10H12BrN3S 284.9935, found 284.9938.
Da ta for 4′-Ch lor op r op iop h en on e Th io Sem ica r ba -
zon e (2f): yield 60%; mp 175.1-176.8 °C; 1H NMR δ 0.99 (t,
3H, J ) 7.6), 2.84 (q, 2H, J ) 7.6), 7.41 (d, 2H, J ) 8.8), 7.95
(d, 2H, J ) 8.4), 7.96 (br s, 1H), 8.30 (br s, 1H), 10.37 (s, 1H);
HRMS (EI) m/z (M+) calcd for C10H12ClN3S 241.0440, found
241.0447.
Da ta for 3′-Br om oa cetop h en on e Th io Sem ica r ba zon e
(3b): mp 174.2-174.9 °C; IR (neat, cm-1) 3428, 3263, 3144,
1
3059, 1604, 1524, 1310, 1116, 871, 802, 732; H NMR δ 2.27
(s, 3H), 7.33 (t, 1H, J ) 8.0), 7.55 (dd, 1H, J ) 1.0, 8.0), 7.88
(d, 1H, J ) 8.0), 8.10 (br s, 1H), 8.18 (s, 1H), 8.31 (br s, 1H),
10.22 (s, 1H); HRMS (EI) m/z (M+) calcd for C9H10BrN3S
270.9779, found 270.9778.
Da ta for 3-Tr iflu or om eth ylben za ld eh yd e Th io Sem i-
ca r ba zon e (3c): mp 220.7-221.7 °C; 1H NMR δ 7.62 (t, 1H,
J ) 7.6), 7.71 (d, 1H, J ) 8.0), 8.02 (d, 1H, J ) 7.6), 8.10 (s,
1H), 8.25 (br s, 1H), 8.26 (s, 1H), 8.28 (br s, 1H), 11.55 (s, 1H);
HRMS (EI) m/z (M+) calcd for C9H8F3N3S 247.0391, found
247.0395.
Da ta for 4′-Meth oxyp r op iop h en on e Th io Sem ica r ba -
1
zon e (2g): mp 117.8-119.8 °C; H NMR δ 0.99 (t, 3H, J )
7.6), 2.83 (q, 2H, J ) 7.6), 3.78 (s, 3H), 6.92 (d, 2H, J ) 9.2),
7.85 (br s, 1H), 7.86 (d, 2H, J ) 8.8), 8.19 (br s, 1H), 10.21 (s,
1H); HRMS (EI) m/z (M+) calcd for C11H15N3OS 237.0936,
found 237.0933.
Da ta for 3-Tr iflu or om eth yla cetop h en on e Th io Sem i-
ca r ba zon e (3d ): mp 197.9-201.2 °C; 1H NMR δ 2.33 (s, 3H),
7.60 (t, 1H, J ) 7.6), 7.72 (d, 1H, J ) 7.6), 8.13 (br s, 1H), 8.22
(m, 2H), 8.34 (br s, 1H), 10.29 (s, 1H); HRMS (EI) m/z (M+)
calcd for C10H10F3N3S 261.0548, found 261.0545.
Da ta for 3′,5′-bis(tr iflu or om eth yl)p r op iop h en on e Th io
Sem ica r ba zon e (2h ): mp 188.0-190.2 °C; IR (neat, cm-1
)
3245, 3153, 2982, 2936, 1596, 1508, 1466, 1392, 1281, 1171,
1126, 893, 866; 1H NMR δ 0.99 (t, 3H, J ) 7.6), 2.98 (q, 2H, t,
3H, J ) 7.6), 8.07 (s, 1H), 8.33 (br s, 1H), 8.43 (br s, 1H), 8.49
(s, 2H), 10.51 (s, 1H); HRMS (EI) m/z (M + H+) calcd for
Da ta for 3,5-Bis(tr iflu or om eth yl)ben za ld eh yd e Th io
1
Sem ica r ba zon e (3e): mp 229.8-230.3 °C; H NMR δ 8.04
C
12H12F6N3S 344.0656, found 344.0671.
(s, 1H), 8.16 (s, 1H), 8.38 (br s, 1H), 8.46 (br s, 1H), 8.54 (s,
2H), 11.71 (s, 1H); HRMS (EI) m/z (M+) calcd for C10H7F6N3S
315.0265, found 315.0269.
Da ta for 3′,4′-Dich lor op r op iop h en on e Th io Sem ica r -
ba zon e (2i): mp 185.6-186.4 °C; IR (neat, cm-1) 3420, 3249,
3150, 3041, 2980, 2942, 1603, 1513, 1475, 1390, 1300, 1101,
1
Da ta for 3′,5′-Bis(tr iflu or om eth yl)a cetop h en on e Th io
Sem ica r ba zon e (3f): mp 238 °C dec; 1H NMR δ 2.38 (s, 3H),
8.06 (s, 1H), 8.36 (br s, 1H), 8.42 (br s, 1H), 8.53 (s, 2H), 10.37
(s, 1H); HRMS (EI) m/z (M+) calcd for C11H9F6N3S 329.0421,
found 321.0429.
1063, 888, 860, 793; H NMR δ 0.98 (t, 3H, J ) 7.6), 2.86 (q,
2H, J ) 7.6), 7.61 (d, 1H, J ) 8.8), 7.85 (dd, 1H, J ) 2.0, 8.6),
8.12 (br s, 1H), 8.22 (d, 1H, J ) 2.0) 8.30 (br s, 1H), 10.35 (s,
1H); HRMS (EI) m/z (M+) calcd for C10H11Cl2N3S 275.0051,
found 275.0053.
Da ta for 3,4-Dich lor oben za ld eh yd e Th io Sem ica r ba -
zon e (3g): 1H NMR δ 7.64 (d, 1H, J ) 8.4), 7.71 (dd, 1H, J )
1.8, 8.4), 7.98 (s, 1H), 8.24 (s, 1H), 8.27 (br s, 1H), 11.55 (s,
1H); HRMS (EI) m/z (M+) calcd for C8H7Cl2N3S 246.9738,
found 246.9732.
Da ta for 2′,4′-Dich lor op r op iop h en on e Th io Sem ica r -
ba zon e (2j): mp 171.8-173.0 °C; 1H NMR δ 1.04 (t, 3H, J )
7.6), 2.49 (q, 2H, J ) 7.6), 7.33 (d, 1H, J ) 8.4), 7.53 (dd, 1H,
J ) 2.0, 8.4), 7.75 (d, 1H, J ) 2.0), 7.77 (br s, 1H), 8.26 (br s,
1H), 9.42 (s, 1H); HRMS (EI) m/z (M+) calcd for C10H11Cl2N3S
275.0051, found 275.0049.
Da ta for 3′,4′-Dich lor oa cetop h en on e Th io Sem ica r ba -
1
Da ta for 3′-Meth oxya cetop h en on e Th io Sem ica r ba -
zon e (3h ): mp 196.0-197.9 °C; H NMR δ 2.27 (s, 3H), 7.61
1
zon e (2k ): mp 195.1-196.7 °C; H NMR δ 2.28 (d, 3H, J )
(d, 1H, J ) 8.8), 7.88 (dd, 1H, J ) 0.8, 8.4), 8.17 (br s, 1H),
3.2), 3.79 (d, 3H, J ) 2.8), 6.95 (d, 1H, J ) 8.0), 7.29 (dt, 1H,
8.27 (s, 1H), 8.34 (br s, 1H), 10.27 (s, 1H); HRMS (EI) m/z (M+)