Vol. 26, No. 18 (2014)
Synthesis of Benzylidene-2-N-(carbothioamido)-6-oxo-1,2,5,6-tetrahydro-1-NH-1,2,4-triazine Derivatives 5933
TABLE-3
SYNTHESIS OF 5a-5l FROM 4a-4l AND MITC
Entry
1
Starting material
Product obtained
Time (min)
120
Yield*
80
m.p. (°C)
> 220
m.w.
274
304
292
319
308
308
336
366
354
381
370
370
4a
4b
4c
4d
4e
4f
5a
5b
5c
5d
5e
5f
2
125
80
> 220
3
120
78
> 220
4
130
80
210-212
> 220
5
125
75
6
125
80
190-192
> 220
7
125
81
4g
4h
4i
5g
5h
5i
8
130
80
> 220
9
140
82
216-218
> 220
10
11
12
120
82
4j
5j
140
81
220-222
160-162
4k
4l
5k
5l
130
80
* Refers to yields of crude products only
TABLE-4
ELEMENTAL ANALYSIS OF 5a-5l
NMR (CDCl3): δ 23.26 (C-CH3), 41.93 (N-CH3), 113.29
(Ar-C=C), 121.24-135.66 (Ar), 146.76 (N-C-CH3), 148.94
(Ar-C=C), 163.05 (C=S), 174. 60 (O=C-N). M+ •1 = 309.
5f: IR (KBr, νmax, cm-1): 3300 (broad, -NH), 3280 (broad,
-NH), 1710 (-C=O), 1280 (C=S); H NMR (400 MHz,
CDCl3/TMS): δ 2.4 (s, 3H, C-CH3), δ 2.6 (s, 3H, N-CH3), δ
Elemental analysis (%)
Compd.
m.f.
m.w.
No.
5a
5b
5c
5d
5e
5f
C
H
N
1
C13H14N4OS
274
304
292
319
308
308
336
366
354
381
370
370
56.91
56.25
53.41
48.89
50.97
50.97
64.26
62.28
61.01
56.68
58.91
58.91
5.30
5.30
4.48
4.10
4.24
4.24
4.79
4.95
4.27
3.90
4.80
4.80
20.42
18.42
19.17
21.93
18.42
18.42
16.65
15.29
15.81
18.42
15.42
15.42
C14H16N4O2S
C13H13N4OSF
C13H13N5O3S
C13H13N4OSCl
C13H13N4OSCl
C18H16N4OS
6.8 (s, 1H, -NH, D2O exchangeable) 7.4-8.4 (m, 6H,Ar-H and
s, 2H, =CH-Ar ), 10.6 (s, 1H, -NH, D2O exchangeable). 13
C
NMR (CDCl3): δ 23.56 (C-CH3), 41.54 (N-CH3), 114.69 (Ar-
C=C), 122.24-137.65 (Ar), 146.69 (N-C-CH3), 148.76 (Ar-
C=C), 163.21 (C=S), 176. 40 (O=C-N). M+ •1 = 309.
5g: IR (KBr, νmax, cm-1) : 2989 (broad, -NH), 3460 (broad,
5g
5h
5i
C19H18N4O2S
C18H15N4OSF
C18H15N5O3S
C18H15N4OSCl
C18H15N4OSCl
1
-NH), 1720 (-C=O), 1292 (C=S); H NMR (400 MHz,
5j
CDCl3/TMS): δ 2.3 (s, 3H, N-CH3), δ 6.4 (s, 1H, -NH, D2O
exchangeable) 7.4-8.4 (m, 11H, Ar-H and s, 2H, =CH-Ar),
10.2 (s, 1H, -NH, D2O exchangeable). 13C NMR (CDCl3): δ
39.34 (N-CH3), 113.29 (Ar-C=C), 121.14-143.45 (Ar), 145.65
(N-C-CH3), 148.46 (Ar-C=C), 162.11 (C=S), 173.20 (O=C-
N). Mass: 221 (20 %), 318 (10 %). M+ •1 = 337.
5k
5l
53.93 (-OCH3), 114.29 (Ar-C=C), 124.13-133.65 (Ar), 146.73
(N-C-CH3), 149.94 (Ar-C=C), 163.31 (C=S), 176. 30 (O=C-
N). Mass: 273 (10 %). M+ •1 = 305.
5h: IR (KBr, νmax, cm-1): 3210 (broad, -NH), 3380 (broad,
1
-NH),1750 (-C=O), 1280 (C=S); H NMR (400 MHz,
5c: IR (KBr, νmax, cm-1): 3445 (broad, -NH), 3051 (broad,
-NH), 1724 (-C=O), 1280 (C=S); 1H NMR (400 MHz, CDCl3/
TMS): δ 2.4 (s, 3H, C-CH3), δ 2.8 (s, 3H, N-CH3), δ 6.6 (s, 1H,
-NH, D2O exchangeable) 7.4-8.4 (m, 5H,Ar-H and s, 2H, =CH-
Ar ), 10.4 (s, 1H, -NH, D2O exchangeable). 13C NMR (CDCl3):
δ 23.26 (C-CH3), 42.24 (N-CH3), 116.59 (Ar-C=C), 123.15-136.
69 (Ar), 144.49 (N-C-CH3), 148.96 (Ar-C=C), 163.04 (C=S),
174. 60 (O=C-N). Mass: 239 (20 %). M+ •1 = 293.
CDCl3/TMS): δ 2.6 (s, 3H, N-CH3), δ 6.9 (s, 1H, -NH, D2O
exchangeable) 7.4-8.4 (m, 10H, Ar-H and s, 2H, =CH-Ar ),
10.3 (s, 1H, -NH, D2O exchangeable). 13C NMR (CDCl3): δ
36.34 (N-CH3), 115.35 (Ar-C=C), 120.34-139.65 (Ar), 146.69
(N-C-CH3), 148.76 (Ar-C=C), 163.21 (C=S), 173.43 (O=C-
N). M+ •1 = 367.
5i: IR (KBr, νmax, cm-1): 3210 (broad, -NH), 3340 (broad,
1
-NH), 1740 (-C=O), 1300 (C=S); H NMR (400 MHz,
5d: IR (KBr, νmax, cm-1): 3283 (broad, -NH), 3251 (broad,
1
-NH), 1726 (-C=O), 1257 (C=S); H NMR (400 MHz,
CDCl3/TMS): δ 2.4 (s, 3H, N-CH3), δ 6.8 (s, 1H, -NH, D2O
exchangeable) 7.4-8.4 (m, 10H, Ar-H and s, 2H, =CH-Ar), 10.6
(s, 1H, -NH, D2O exchangeable). 13C NMR (CDCl3): 42.54 (N-
CH3), 113.49 (Ar-C=C), 121.24-139.65 (Ar), 146.56 (N-C-CH3),
147.76 (Ar-C=C), 164.21 (C=S), 175. 40 (O=C-N). M+ •1 = 355.
5j: IR (KBr, νmax, cm-1): 3210 (broad, -NH), 3330 (broad,
CDCl3/TMS): δ 1.8 (s, 3H, C-CH3), δ 2.3 (s, 3H, N-CH3), δ
6.6 (s, 1H, -NH, D2O exchangeable) 7.4-8.4 (m, 5H,Ar-H and
s, 2H, =CH-Ar ), 10.2 (s, 1H, -NH, D2O exchangeable). 13
C
NMR (CDCl3): δ 23.63 (C-CH3), 41.93 (N-CH3), 115.39
(Ar-C=C), 121.13-136.62 (Ar), 146.74 (N-C-CH3), 148.93 (Ar-
C=C), 163.04 (C=S), 179.78 (O=C-N). Mass: 273 (10 %).
M+ •1 = 320.
5e: IR (KBr, νmax, cm-1): 3307 (broad, -NH), 3198 (broad,
1
-NH) 1729 (-C=O), 1255 (C=S); H NMR (400 MHz,
1
-NH), 1740 (-C=O), 1280 (C=S); H NMR (400 MHz,
CDCl3/TMS): δ 2.6 (s, 3H, N CH3), δ 6.4 (s, 1H, -NH, D2O
exchangeable) 7.4-8.4 (m, 10H, Ar-H and s, 2H, =CH-Ar),
10.7 (s, 1H, -NH, D2O exchangeable). 13C NMR (CDCl3): 40.35
(N-CH3), 113.56 (Ar-C=C), 124.24-142.65 (Ar), 146.68 (N-
C-CH3), 148.74 (Ar-C=C), 162.22 (C=S), 174. 43 (O=C-N).
M+ •1 = 382.
CDCl3/TMS): δ 1.8 (s, 3H, C-CH3), δ 2.4 (s, 3H, N-CH3), δ
6.6 (s, 1H, -NH, D2O exchangeable) 7.4-8.4 (m, 5H,Ar-H and
s, 2H, =CH-Ar ), 10.2 (s, 1H, -NH, D2O exchangeable). 13
C