Journal of Chemistry
5
(-CONH-), 153.1 (C-3); 152.1 (C-5ꢀ), 149.7 (C-4ꢀ), 141.1 (C-
(C-3ꢀ), 56.7 (5ꢀ-OCH ), 56.6 (4ꢀ-OCH ), 48.9 (C-5), 46.5
3
3
2ꢀ), 122.4 (C-1ꢀ), 112.0 (C-6ꢀ), 108.0 (C-3ꢀ), 56.8 (5ꢀ-OCH ),
(-CH -CH -CH ), 34.5 (C-4), 22.5 (-CH -CH CH ), 11.4
3
2
2
3
2
2
3
56.7 (4ꢀ-OCH ), 45.5 (C-5), 35.1 (C-4), 34.9 (-CH -CH ), 15.7
(-CH -CH -CH ). MS (LSIMS): ꢃ/ꢄ 353.1274 [M + H]+,
3
2
3
2
2
3
(-CH -CH ). MS (LSIMS): ꢃ/ꢄ 323.1348 [M + H]+, Calcd.
Calcd. Mass for C H N O S 353.1284.
2
3
15 21
4
4
Mass for C H N O 323.1355.
14 19
4
5
N-Ethyl-3-(6-nitro-2,3,4-trimethoxyphenyl)-4,5-dihydro-1H-
pyrazole-1-carboxamide, (34l). Yellow solid, yield 472 mg
(1.340 mmol) (67%). Mp: 126–128∘C. 1H NMR (499.79 MHz,
3-(4,5-Dimethoxy-2-nitrophenyl)-N-propyl-4,5-dihydro-1H-
pyrazole-1-carboxamide (34h). White solid, yield 464 mg
(1.380 mmol) (69%). Mp: 144-145∘C. 1H NMR (499.79 MHz,
CDCl ): ꢁ/ppm 7.40 (s, 1H, H-5ꢀ), 5.69 (bs, 1H, -CO-), 4.05 (t,
3
CDCl ): ꢁ/ppm 7.39 (s, 1H, H-3ꢀ), 6.80 (s, 1H, H-6ꢀ), 5.81
2H, H-5, ꢂ = 10.3 Hz), 3.98, 3.96, 3.89 (3s, 9H, 2ꢀ-OCH , 3ꢀ-
3
3
(m, 1H, -NH-), 3.87 (t, 2H, H-5, ꢂ = 10.3 Hz), 3.86 (s, 3H,
OCH , 4ꢀ-OCH ), 3.30 (m, 2H, -CH -CH ), 3.18 (t, 2H, H-4,
3
3
2
3
3
5ꢀ-OCH ), 3.82 (s, 3H, 4ꢀ-OCH ), 3.08 (m, 2H, -CH -CH -
ꢂ = 10.3 Hz), 1.14 (t, 3H, -CH -CH , ꢂ = 7.2 Hz). 13C NMR
3
3
2
2
2
3
2
CH ), 2.93 (t, 2H, H-4, ꢂ = 10.3 Hz), 1.40 (m, 2H, -CH -CH -
(125.69 MHz, CDCl ): ꢁ/ppm 155.25 (C-3), 153.7 (-CONH-),
3
2
2
3
CH ), 0.78 (t, 3H, -CH -CH -CH , ꢂ = 7.4 Hz). 13C NMR
152.4 (C-4ꢀ), 149.1 (C-3ꢀ), 146.5 (C-6ꢀ), 143.6 (C-2ꢀ), 116.6
3
2
2
3
(125.69 MHz, CDCl ): ꢁ/ppm 155.2 (-CONH-), 152.6 (C-3),
(C-1ꢀ), 104.1 (C-5ꢀ), 62.0, 61.0 (2ꢀ-OCH , 3ꢀ-OCH ), 56.5
3
3
151.6 (C-5ꢀ), 149.3 (C-4ꢀ), 140.7 (C-2ꢀ), 121.8 (C-1ꢀ), 111.7 (C-
(4ꢀ-OCH ), 45.1 (C-5), 36.4 (-CH -CH ), 34.7 (C-4), 15.3
3
3
6ꢀ), 107.5 (C-3ꢀ), 56.4 (5ꢀ-OCH ), 56.3 (4ꢀ-OCH ), 45.1 (C-5),
(-CH -CH ). MS (LSIMS): ꢃ/ꢄ 353.1456 [M + H]+, Calcd.
3
3
2
3
41.6 (-CH -CH -CH ), 34.4 (C-4), 23.3 (-CH -CH -CH ),
Mass for C H N O 353.1461.
2
2
3
2
2
3
15 21
4
6
11.1 (-CH -CH -CH ). MS (LSIMS): ꢃ/ꢄ 337.1527 [M + H]+,
2
2
3
Calcd. Mass for C H N O 337.1512.
3-(6-Nitro-2,3,4-trimethoxyphenyl)-N-propyl-4,5-dihydro-1H-
pyrazole-1-carboxamide (34m). Yellow solid, yield 506 mg
(1.380 mmol) (69%). Mp: 132–135∘C. 1H NMR (400.17 MHz,
15 21
4
5
3-(4,5-Dimethoxy-2-nitrophenyl)-N-methyl-4,5-dihydro-1H-
pyrazole-1-carbothioamide (34i). Brown solid, yield 441 mg
(1.360 mmol) (68%). Mp: 179–181∘C. 1H NMR (499.79 MHz,
CDCl ): ꢁ/ppm 7.39 (s, 1H, H-5ꢀ), 5.74 (bs, 1H, -CO-), 4.03 (t,
3
H-5, ꢂ = 10.3 Hz), 3.96, 3.95, 3.88 (3s, 9H, 2ꢀ-OCH , 3ꢀ-OCH ,
3
3
CDCl ): ꢁ/ppm 7.59 (s, 1H, H-3ꢀ), 7.17 (bs, 1H, -NH-), 6.89
4ꢀ-OCH ), 3.20 (t, H-4, ꢂ = 10.3 Hz), 3.11 (m, 2H, -CH -CH -
3
3
2
2
(s, 1H, H-6ꢀ), 4.40 (t, 2H, H-5, ꢂ = 10.0 Hz), 3.99 (s, 3H, 5ꢀ-
CH ), 1.50 (m, 2H, -CH -CH -CH ), 0.91 (t, 3H, -CH -CH -
3
2
2
3
2
2
OCH ), 3.98 (s, 3H, 4ꢀ-OCH ), 3.16 (d, 3H, -CH , ꢂ = 4.8 Hz),
CH , ꢂ = 7.4 Hz). 13C NMR (125.69 MHz, CDCl ): ꢁ/ppm
3
3
3
3
3
3.13 (t, 2H, H-4, ꢂ = 10.0 Hz). 13C NMR (125.69 MHz, CDCl ):
155.9 (C-3), 153.6 (-CONH-), 152.3 (C-4ꢀ), 149.4 (C-3ꢀ), 146.5
(C-6ꢀ), 143.6 (C-2ꢀ), 116.4 (C-1ꢀ), 104.1 (C-5ꢀ), 62.1, 61.1 (2ꢀ-
OCH , 3ꢀ-OCH ), 56.8 (4ꢀ-OCH ), 44.9 (C-5), 41.8 (-CH -
3
ꢁꢀ/ppm 177.50 (-CSNH-), 155.8 (C-3), 153.1 (C-5ꢀ), 150.0 (C-
4 ), 141.0 (C-2ꢀ), 121.6 (C-1ꢀ), 111.8 (C-6ꢀ), 108.0 (C-3ꢀ), 56.8
(5ꢀ-OCH ), 56.6 (4ꢀ-OCH ), 49.2 (C-5), 34.7 (C-4), 31.6 (-
3
3
3
2
CH -CH ), 36.2 (C-4); 23.2 (-CH -CH -CH ), 11.2 (-CH -
3
3
2
3
2
2
3
2
CH ). MS (LSIMS): ꢃ/ꢄ 347.0800 [M + Na]+, Calcd. Mass
CH -CH ). MS (LSIMS): ꢃ/ꢄ 389.1436 [M + Na]+, Calcd.
3
2
3
for C H N O NaS 347.0790.
Mass for C H N O Na 389.1437.
13 16
4
4
16 22
4
6
3-(4,5-Dimethoxy-2-nitrophenyl)-N-ethyl-4,5-dihydro-1H-
pyrazole-1-carbothioamide (34j). Yellow solid, yield 474 mg
(1.400 mmol) (70%). Mp: 194-195∘C. 1H NMR (499.79 MHz,
3-(6-Nitro-2,3,4-trimethoxyphenyl)-N-phenyl-4,5-dihydro-1H-
pyrazole-1-carboxamide (34n). Yellow solid, yield 536 mg
(1.340 mmol) (67%). Mp: 140–142∘C. 1H NMR (400.17 MHz,
CDCl ): ꢁ/ppm 7.60 (s, 1H, H-3ꢀ), 7.12 (m, 1H, -NH-), 6.89
CDCl ): ꢁ/ppm 7.73 (bs, 1H, -CONH-), 7.44 (d, 2H, H-2ꢀꢀ,
3
3
3
(s, 1H, H-6ꢀ), 4.40 (t, 2H, H-5, ꢂ = 10.2 Hz), 4.00 (s, 3H,
H-6ꢀꢀ, ꢂ = 7.7 Hz), 7.42 (s, 1H, H-5ꢀ), 7.26 (t, 2H, H-3ꢀꢀ, H-
5ꢀꢀ, ꢂ = 7.9 Hz), 6.99 (t, 1H, H-4ꢀꢀ, ꢂ = 7.4 Hz), 4.12 (t, 2H,
5ꢀ-OCH ), 3.98 (s, 3H, 4ꢀ-OCH ), 3.69 (m, 2H, -CH -CH ),
3
3
2
3
3
3.13 (t, 2H, H-4, ꢂ = 10.2 Hz), 1.24 (t, 3H, -CH -CH , ꢂ
H-5, ꢂ5-4 = 10.3 Hz), 3.97, 3.96, 3.91 (3s, 9H, 2ꢀ-OCH , 3ꢀ-
2
3
3
= 7.2 Hz). 13C NMR (125.69 MHz, CDCl ): ꢁ/ppm 176.4
OCH , 4ꢀ-OCH ), 3.25 (t, 2H, H-4, ꢂ4-5 = 10.3 Hz). 13C NMR
3
3
(-CSNH-), 155.8 (C-3), 153.2 (C-5ꢀ), 150.0 (C-4ꢀ), 141.0 (C-2ꢀ),
(100.73 MHz, CDCl ): ꢁ/ppm 153.9 (C-3), 152.3 (-CONH-);
3
121.7 (C-1ꢀ), 111.9 (C-6ꢀ), 108.0 (C-3ꢀ), 56.9 (5ꢀ-OCH ), 56.7
152.2 (C-4ꢀ); 150.3 (C-3ꢀ); 146.7 (C-6ꢀ); 143.5 (C-2ꢀ); 138.5 (C-
1ꢀꢀ); 128.8 (C-3ꢀꢀ, C-5ꢀꢀ), 122.8 (C-4ꢀꢀ), 118.9 (C-2ꢀꢀ, C-6ꢀꢀ), 116.2
(C-1ꢀ), 104.2 (C-5ꢀ), 62.1, 61.2 (2ꢀ-OCH , 3ꢀ-OCH ), 56.6 (4ꢀ-
(4ꢀ-OCH ), 49.1 (C-5), 39.7 (-CH -CH ), 34.7 (C-4), 14.7
3
2
3
(-CH -CH ). MS (LSIMS): ꢃ/ꢄ 339.1141 [M + H]+, Calcd.
2
3
3
3
Mass for C H N O S 339.1127.
OCH ), 44.6 (C-5), 36.5 (C-4). MS (LSIMS): ꢃ/ꢄ 401.1464
14 19
4
4
3
[M + H]+, Calcd. Mass for C H N O 401.1461.
15 21
4
6
3-(4,5-Dimethoxy-2-nitrophenyl)-N-propyl-4,5-dihydro-1H-
pyrazole-1-carbothioamide (34k). Yellow solid, yield 458 mg
(1.300 mmol) (65%). Mp: 155-156∘C. 1H NMR (499.79 MHz,
N-Methyl-3-(6-nitro-2,3,4-trimethoxyphenyl)-4,5-dihydro-1H-
pyrazole-1-carbothioamide (34o). Yellow solid, yield 482 mg
(1.360 mmol) (68%). Mp: 122–125∘C. 1H NMR (400.17 MHz,
CDCl ): ꢁ/ppm 7.54 (s, 1H, H-3ꢀ), 7.16 (m, 1H, -NH-), 6.88
3
(s, 1H, H-6ꢀ), 4.35 (t, 2H, H-5, ꢂ = 10.0 Hz), 3.97 (s, 3H,
CDCl ): ꢁ/ppm 7.44 (s, 1H, H-5ꢀ), 7.04 (s, 1H, -CSNH-), 4.43
3
5ꢀ-OCH ), 3.95 (s, 3H, 4ꢀ-OCH ), 3.55 (m, 2H, -CH -CH -
(t, 2H, H-5, ꢂ5-4 = 9.9 Hz), 3.98, 3.98, 3.90 (3s, 9H, 2ꢀ-OCH ,
3
3
2
2
3
CH ), 3.10 (t, 2H, H-4, ꢂ = 10.0 Hz), 1.61 (m, 2H, -CH -CH ),
3ꢀ-OCH , 4ꢀ-OCH ), 3.23 (t, 2H, H-4, ꢂ4-5 = 9.9 Hz), 3.14
3
2
3
3
3
0.92 (t, 3H, CH , ꢂ = 7.4 Hz). 13C NMR (125.69 MHz,
(d, 3H, -CH , ꢂ = 4.7 Hz). 13C NMR (100.73 MHz, CDCl ):
3
3
3
CDCl ): ꢁ/ppm 176.3 (-CSNH-), 155.5 (C-3), 153.0 (C-5ꢀ),
ꢁ/ppm 177.1 (-CSNH-), 154.0 (C-3), 153.6 (C-4ꢀ), 152.2 (C-3ꢀ),
3
149.9 (C-4ꢀ), 140.9 (C-2ꢀ), 121.4 (C-1ꢀ), 111.8 (C-6ꢀ), 107.8
146.8 (C-6ꢀ), 143.2 (C-2ꢀ), 115.9 (C-1ꢀ), 104.2 (C-5ꢀ), 62.2, 61.2