1626
Biol. Pharm. Bull.
Vol. 38, No. 10 (2015)
to afford the corresponding hydrazones 21a–h with 65–80% [(M+2)+, 4.6], 454 [M+, 11.8], 105 [100]; MS m/z [%]: 430
yield.
(1Z,2E)-2-(2-(5-Nitrofuran-2-carbonyl)hydrazono)-N′-
[(M+2)+, 1.2], 428 [M+, 3.0], 64 [100].
(1Z,2E)-2-(2-(5-Nitrofuran-2-carbonyl)hydrazono)-N′-
phenylpropanehydrazonoyl Chloride (21a) Orange pow- (4-(N-thiazol-2-ylsulfamoyl)phenyl)propanehydrazonoyl
der (yield 75%), mp 230°C; IR (KBr, ν cm−1): 3414, 3315 Chloride (21g) Orange powder (yield 75%), mp 233°C;
1
(2NH), 1668 (C=O) and 1599 (C=N); H-NMR (DMSO-d6) IR (KBr, ν cm−1): 3419–3253 (3NH), 1682 (C=O) and 1597
1
δ ppm: 2.38 (s, 3H, CH3), 6.94–7.98 (m, 7H, ArH), 10.27 (s, (C=N); H-NMR (DMSO-d6) δ ppm: 2.38 (s, 3H, CH3), 6.82
D2O exch., 1H, =NNH–), 11.10 and 11.55 (s, D2O exch., 1H, (d, J=3Hz, 1H, H5 of thiazole), 7.25 (d, J=3Hz, 1H, H4 of
–CONH–); MS m/z [%]: 351 [(M+2)+, 9.3], 349 [M+, 26.9], 92 thiazole), 7.45 (d, J=7.5Hz, 2H, Ar-H), 7.54-7.96 (m, 4H,
[100].
ArH), 10.63 (s, D2O exch., 1H, =NNH–), 10.96 and 11.61 (s,
(1Z,2E)-N′-(4-Fluorophenyl)-2-(2-(5-nitrofuran-2- D2O exch., 1H, –CONH–), 12.65 (s, D2O exch., 1H, SO2NH-);
carbonyl)hydrazono)propanehydrazonoyl Chloride (21b) 13C-NMR (DSMO-d6) δ ppm: 25.90, 108.41, 113.50, 114.01,
Orange powder (yield 75%), mp 232°C; IR (KBr, ν cm−1): 115.04, 124.86, 125.14, 127.99, 134.77, 136.24, 145.90, 146.74,
1
3420, 3317 (2NH), 1652 (C=O) and 1589 (C=N); H-NMR 153.50, 156.00, 188.57; MS m/z [%]: 511 [M+, 0.1], 111 [100].
(DMSO-d6) δ ppm: 2.36 (s, 3H, CH3), 7.13 (t, J=7.5Hz, 2H,
(1Z,2E)-2-(2-(5-Nitrofuran-2-carbonyl)hydrazono)-
Ar-H), 7.36–7.97 (m, 4H, ArH), 10.29 (s, D2O exch., 1H, N'-(4-(N-pyrimidin-2-ylsulfamoyl)phenyl)propanehydra-
=NNH–), 11.10 and 11.54 (s, D2O exch., 1H, –CONH–); zonoyl Chloride (21h) Orange powder (yield 75%), mp
13C-NMR (DSMO-d6)
δ
ppm: 19.02, 113.48, 115.66 236°C; IR (KBr, ν cm−1): 3481–3246 (3NH), 1696 (C=O) and
1
(3JF-C=7.5 Hz), 116.11(2JF-C=22.5Hz), 122.15, 123.50, 127.00, 1597 (C=N); H-NMR (DMSO-d6) δ ppm: 2.38 (s, 3H, CH3),
140.46 (2C), 152.53, 156.83 (1JF-C=236.3Hz), 157.41; MS m/z 7.05 (m, 1H, Ar-H), 7.47 (d, J=8.25Hz, 1H, H4 of furan), 7.57
[%]: 369 [(M+2)+, 7.0], 367 [M+, 18.9], 110 [100].
(d, J=8.5Hz, 2H, Ar-H), 7.81 (s, D2O exch., 1H, SO2NH-),
(1Z,2E)-N′-(4-Chlorophenyl)-2-(2-(5-nitrofuran-2- 7.91 (d, J=8.25Hz, 1H, H5 of furan), 7.95 (d, J=8.5Hz, 2H,
carbonyl)hydrazono)propanehydrazonoyl Chloride (21c) Ar-H), 8.51 (d, J=7.0Hz, 2H, Ar-H), 10.69 (s, D2O exch.,
Red powder (yield 75%), mp 231°C; IR (KBr, ν cm−1): 3414, 1H, =NNH–), 11.00 and 11.62 (s, D2O exch., 1H, –CONH–);
3319 (2NH), 1669 (C=O) and 1595 (C=N); H-NMR (DMSO- 13C-NMR (DSMO-d6) δ ppm: 25.92, 113.80, 114.83, 116.24,
1
d6) δ ppm: 2.36 (s, 3H, CH3), 7.35–7.96 (m, 6H, ArH), 10.39 125.53, 129.00, 129.96, 132.25, 133.82, 146.59, 147.42, 157.42,
(s, D2O exch., 1H, =NNH–), 11.15 and 11.56 (s, D2O exch., 157.48, 158.82, 188.62; MS m/z [%]: 506 [M+, 2.4], 64 [100].
1H, –CONH–); 13C-NMR (DSMO-d6) δ ppm: 13.88, 113.47,
Synthesis of Target Compounds 22a–e The sulfone
115.94, 122.13, 125.32, 129.46, 142.86, 146.91, 152.56, 147.33, derivatives 20a–e (1mmol) was added to a suspension of the
148.81, 154.89; MS m/z [%]: 387 [(M+4)+, 1.4 ], 385 [(M+2)+, 5-nitrofuran-2-carbohydrazide 11 (1mmol) in absolute ethanol
8.3], 383 [M+, 12.6], 126 [100].
(10mL), and glacial acetic acid (0.5mL) was added to the
(1Z,2E)-2-(2-(5-Nitrofuran-2-carbonyl)hydrazono)-N′- mixture. The reaction mixture refluxed for 0.5h. The precipi-
p-tolylpropanehydrazonoyl Chloride (21d) Red powder tate formed was collected by filtration while hot, washed with
(yield 75%), mp 239°C; IR (KBr, ν cm−1): 3420, 3315 (2NH), hot ethanol, dried and crystallized from EtOH/DMF to afford
1
1668 (C=O) and 1576 (C=N); H-NMR (DMSO-d6) δ ppm: compounds 22a–e.
2.25 (s, 3H, CH3), 2.35 (s, 3H, CH3), 7.10 (d, J=6Hz, 2H,
(E)-5-Nitro-N′-(1-phenyl-2-(phenylsulfonyl)ethylidene)-
Ar-H), 7.24 (d, J=6Hz, 2H, Ar-H), 7.68–7.97 (m, 2H, H3 and furan-2-carbohydrazide (22a) Yellow powder (yield 75%),
H4 of furan), 10.17 (s, D2O exch., 1H, =NNH–), 11.09 and mp 233°C; IR (KBr, ν cm−1): 3420, 3278 (2NH), 1700 (C=O),
11.52 (s, D2O exch., 1H, –CONH–); 13C-NMR (DSMO-d6) 1591 (C=N) and 1354, 1150 (SO2); 1H-NMR (DMSO-d6) δ
δ ppm: 13.82, 20.76, 113.47, 114.39, 115.32, 122.43, 130.02, ppm: 5.36 and 5.44 (s, 2H, CH2), 7.40–7.91 (m, 12H, ArH),
141.57, 146.47, 147.11, 147.40, 152.49, 157.40; MS m/z [%]: 365 11.14 and 11.66 (s, D2O exch., 1H, –CONH–); MS m/z [%]: 414
[(M+2)+, 9.8], 363 [M+, 28.8], 106 [100].
[(M+1)+, 1.1], 413 [M+, 3.2], 272 [100].
(1Z,2E)-N′-(4-Methoxyphenyl)-2-(2-(5-nitrofuran-2-
(E)-N′-(1-(4-Fluorophenyl)-2-(Phenylsulfonyl)-
carbonyl)hydrazono)propanehydrazonoyl Chloride (21e) ethylidene)-5-nitrofuran-2-carbohydrazide (22b) Yellow
Brown powder (yield 75%), mp 224°C; IR (KBr, ν cm−1): powder (yield 75%), mp 255°C; IR (KBr, ν cm−1): 3419,
3414, 3318 (2NH), 1668 (C=O) and 1576 (C=N); 1H-NMR 3284 (2NH), 1700 (C=O), 1590 (C=N) and 1307, 1154 (SO2);
(DMSO-d6) δ ppm: 2.35 (s, 3H, CH3), 3.73 (s, 3H, OCH3), 1H-NMR (DMSO-d6) δ ppm: 5.36 and 5.46 (s, 2H, CH2),
6.90 (d, 2H, Ar-H, J=7.5Hz), 7.29 (d, 2H, Ar-H, J=7.5Hz), 7.22–7.89 (m, 11H, ArH), 11.13 and 11.67 (s, D2O exch., 1H,
7.70–7.98 (m, 2H, H3 and H4 of furan), 10.13 (s, D2O exch., –CONH–); MS m/z [%]: 432 [(M+1)+, 1.6], 431 [M+, 5.0], 290
1H, =NNH–), 11.10 and 11.51 (s, D2O exch., 1H, –CONH–); [100].
MS m/z [%]: 381 [(M+2)+, 3.5], 379 [M+, 10.2], 122 [100].
(E)-N′-(1-(4-Chlorophenyl)-2-(phenylsulfonyl)-
(1Z,2E)-2-(2-(5-Nitrofuran-2-carbonyl)hydrazono)-N′- ethylidene)-5-nitrofuran-2-carbohydrazide (22c) Yellow
(4-sulfamoylphenyl)propanehydrazonoyl Chloride (21f) powder (yield 75%), mp 223°C; IR (KBr, ν cm−1): 3414,
Red powder (yield 75%), mp 260°C; IR (KBr, ν cm−1): 3289 (2NH), 1697 (C=O), 1592 (C=N) and 1353, 1153 (SO2);
3390–3264 (2NH,NH2), 1670 (C=O) and 1596 (C=N); 1H-NMR (DMSO-d6) δ ppm: 5.36 and 5.45 (s, 2H, CH2),
1H-NMR (DMSO-d6) δ ppm: 2.37 (s, 3H, CH3), 7.20 (s, D2O 7.46–7.97 (m, 11H, ArH), 11.14 and 11.67 (s, D2O exch., 1H,
exch., 2H, SO2NH2), 7.46 (d, J=7.5Hz, 2H, Ar H), 7.75–7.95 –CONH–); 13C-NMR (DSMO-d6) δ ppm: 62.70, 114.50,
(m, 4H, ArH), 10.59 (s, D2O exch., 1H, =NNH–), 11.14 and 119.00, 128.48, 128.66, 128.80, 129.34, 129.55, 129.70, 131.42,
11.57 (s, D2O exch., 1H, –CONH–); 13C-NMR (DSMO-d6) 134.51, 134.88, 139.84, 152.49, 188.62; MS m/z [%]: 449
δ ppm: 19.00, 113.98, 115.01, 122.20, 125.29, 127.74, 136.75, [(M+2)+, 2.6], 447 [M+, 6.0], 139 [100].
138.19, 145.66, 152.51, 157.46, 188.56; MS m/z [%]: 456
(E)-5-Nitro-N′-(1-(4-nitrophenyl)-2-tosylethylidene)fu-