572 JOURNAL OF CHEMICAL RESEARCH 2015
sodium acetate (0.164 g, 20mmol) in acetic acid (30 mL) was refluxed
for 6 h. The solid product which formed on heating was collected and
recrystallised from acetic acid to give 10–12, respectively.
CDCl ): δ 14.34 (CH ), 54.34 (CH ), 67.10 (CH ), 128.30 (1ArC),
3 3 2 2
128.45 (2ArC), 128.54 (1ArC), 128.62 (1ArC), 129.35 (2ArC), 129.57
(2ArC), 129.84 (2ArC), 130.43 (2ArC), 131.05 (1ArC), 131.10 (2ArC),
134.88 (1ArC), 141.02 (1ArC), 153.62 (=CH), 154.57 (C-6, triazine),
155.53 (C-5, triazine), 164.62 (C=N), 165.62, 168.4 (2 C=O), 169.45
(C-3, triazine). Anal. calcd for C H N O S : C, 64.67; H, 4.12; N,
5
-(4-[(5,6-Diphenyl-1,2,4-triazin-3-yl)thio]benzylidene)-3-
phenyl-2-thioxothiazolidin-4-one (10): Yellow solid; yield 74%; m.p.
-
1
2
(
88–289ºC; IR (potassium bromide, cm ): 3047 (CH-arom), 1714
2
9
22
4
3 2
1
C=O), 1601 (C=N), 1244, 1083 (C=S); H NMR (600 MHz, CDCl ):
δ 7.26–7.81 (m, 19H, ArH), 7.88 (s, 1H, CH–benzylidene). C NMR
10.40; found: C, 64.45; H, 4.03; N, 10.30%.
3
13
Synthesis of compounds 19 and 20; general procedure
A mixture of compound 4b (4.42 g, 10 mmol), ethyl chloroacetate
(
150 MHz, CDCl ): δ 124.70 (=C), 128.38 (2ArC), 128.58 (1ArC),
3
128.67 (1ArC), 129.34 (2ArC), 129.65 (2ArC), 129.67 (2ArC), 129.82
(
1.22 g, 10 mmol) or chloroacetone (0.92 g, 10 mmol) and sodium
acetate (0.164 g, 20mmol) in acetic acid (30 mL) was refluxed for
h. The solid product which formed on heating was collected and
recrystallised from the proper solvents.
-(2-(4-[(5,6-Diphenyl-1,2,4-triazin-3-yl)thio]benzylidene)
hydrazinyl)thiazol-4(5H)-one (19): Faint yellow solid (dioxane);
(
1
(
1
2ArC), 129.84 (2ArC), 131.14 (2ArC), 131.19 (1ArC), 131.70 (2ArC),
32.11 (1ArC), 134.19 (1ArC), 134.79 (1ArC), 134.86 (1ArC), 135.01
1ArC), 135.66 (=CH), 154.57 (C-6, triazine), 155.76 (C-5, triazine),
67.52 (C=O), 170.16 (C-3, triazine), 192.94 (C=S). Anal. calcd for
C H N OS : C, 66.41; H, 3.60; N, 9.99; found: C, 66.29; H, 3.44; N,
4
2
31
20
4
3
9.82%.
-1
yield 73%; m.p. 260–261 ºC; IR (potassium bromide, cm ): 3150
(
5
- (4-[(5,6-Diphenyl-1,2,4-triazin-3-yl)thio]benzylidene) -
1
NH), 2942, 2850 (aliph. CH), 1720 (C=O), 1584 (C=N); H NMR
2
2
1
-iminothiazolidin-4-one (11): Yellow solid; yield 71%; m.p.
(
8
600 MHz, DMSO-d ): δ 3.72 (s, 2H, CH ), 7.20–7.81 (m, 14H, ArH),
-1
6
2
49–251 ºC; IR (potassium bromide, cm ): 3189 (NH), 1665 (C=O),
.35 (s, 1H, CH–benzylidene), 11.93 (s, 1H, NH). Anal. calcd for
1
587 (C=N); H NMR (600 MHz, DMSO-d ): δ 7.16–7.79 (m, 15H,
6
C H N OS : C, 62.22; H, 3.76; N, 17.42; found: C, 62.03; H, 3.71; N,
13
25 18
6
2
ArH + CH–benzylidene), 9.86, 10.00 (2s, 2H, 2NH). C NMR (150
1
7.34%.
-(2-(4-[(5,6-Diphenyl-1,2,4-triazin-3-yl)thio]benzylidene)
hydrazinyl)-4-methyl-thiazole (20): Brown solid (dioxane); yield
MHz, CDCl ): δ 127.81 (2ArC), 128.08 (1ArC), 128.20 (1ArC), 128.68
3
2
(
1
1
2ArC), 128.81 (2ArC), 129.17 (2ArC), 129.34 (2ArC), 129.70 (2ArC),
34.31 (1ArC), 135.10 (1ArC), 135.26 (=CH), 153.99 (C-6, triazine),
55.31 (C-5, triazine), 175.73 (C-3, triazine), 180.67 (C=O).Anal. calcd
for C H N OS : C, 64.22; H, 3.66; N, 14.98; found: C, 64.04; H, 3.47;
-1
67%; m.p. 285–286ºC; IR (potassium bromide, cm ): 3115 (NH), 3059
1
(
3
arom. CH), 1595 (C=N); H NMR (600 MHz, DMSO-d ): δ 2.16 (s,
6
2
5
17
5
2
H, CH ), 6.08 (s, 1H, thiazole-H), 7.18–7.90 (m, 14H, ArH), 8.35 (s,
3
N, 14.75%.
-(4-[(5,6-Diphenyl-1,2,4-triazin-3-yl)thio]benzylidene)-2-(phenyl-
imino)thiazolidin-4-one (12): Yellow solid; yield 68%; m.p. 235–236ºC;
1
H, CH–benzylidene), 11.93 (s, 1H, NH). Anal. calcd for C H N S :
2
6
20
6 2
5
C, 64.98; H, 4.19; N, 17.49; found: C, 64.84; H, 4.14; N, 17.42%.
-1
IR (potassium bromide, cm ): 3178 (NH), 1671 (C=O), 1600 (C=N);
Synthesis of 21 and 22; general procedure
1
H NMR (600 MHz, DMSO-d ): δ 6.97-7.80 (m, 20H, ArH + CH–
A mixture of compound 19 (4.82 g, 10 mmol), 4-methoxybenzaldeyde
(1.36 g, 10 mmol) or isatin (1.47 g, 10 mmol) and sodium acetate
(0.164 g, 20mmol) in acetic acid (30 mL) was refluxed for 3 h. The
solid product which formed on heating was collected and recrystallised
from the proper solvents.
6
13
benzylidene), 8.00 (s, 1H, 1NH). C NMR (150 MHz, DMSO-d ): δ
6
1
(
1
(
20.57 (C-5), 121.18 (2ArC), 128.11 (1ArC), 128.16 (2ArC), 128.27
2ArC), 128.73 (2ArC), 128.91 (2ArC), 129.10 (2ArC), 129.24 (2ArC),
29.41 (2ArC), 129.94 (2ArC), 134.74 (1ArC), 135.12 (1ArC), 140.16
=CH), 154.93 (C-6, triazine), 155.27 (C-5, triazine), 165.56 (C-2),
2-(2-(4-[(5,6-Diphenyl-1,2,4-triazin-3-yl)thio]benzylidene)
hydrazinyl)-5-(4-methoxy-benzylidene)thiazol-4(5H)-one (21): yellow
solid (dioxane); yield 81%; m.p. 297–298 ºC; IR (potassium bromide,
1
70.52 (C-3, triazine), 174.13 (C=O). Anal. calcd for C H N OS : C,
31
21
5
2
68.49; H, 3.89; N, 12.88; found: C, 68.32; H, 3.66; N, 12.71%.
-1
1
cm ): 3160 (NH), 2940 (aliph. CH), 1729 (C=O), 1619 (C=N); H NMR
Synthesis of 16–18; general procedure
(
8
600 MHz, DMSO-d ): δ 3.77 (s, 3H, OCH ), 7.23–7.80 (m, 18H, ArH),
6
3
A mixture of 3 (3.69 g, 10 mmol), 2-(4-oxothiazolidin-2-ylidene)
acetonitrile 13 (1.4 g, 10 mmol) or 2-(4-oxothiazolidin-2-ylidene)
acetamide 14 (1.58 g, 10 mmol) or ethyl 2-(4-oxothiazolidin-2-ylidene)
acetate 15 (1.87 g, 10 mmol) in ethanol (30 mL) containing a few drops
of piperidine was refluxed for 4 h. The solid product which formed on
heating was collected and recrystallised from acetic acid to give 16–18,
respectively.
.01 (s, 1H, CH–benzylidene), 8.36 (s, 1H, CH=N), 11.94 (s, 1H, NH).
Anal. calcd for C H N O S : C, 65.98; H, 4.03; N, 13.99; found: C,
33
24
6
2 2
65.84; H, 3.92; N, 13.92%.
2
-(2-(4-[(5,6-Diphenyl-1,2,4-triazin-3-yl)thio]benzylidene)
hydrazinyl)-5-(2-oxoindolin-3-ylidene)thiazol-4(5H)-one (22): Yellow
-1
solid (dioxane); yield 83%; m.p. 300 ºC; IR (potassium bromide, cm ):
1
3
164 (NH), 1700 (C=O), 1613 (C=N); H NMR (600 MHz, DMSO-d ):
6
2
-(5-(4-[(5,6-Diphenyl-1,2,4-triazin-3-yl)thio]benzylidene)-4-oxo-
δ 6.77–7.74 (m, 18H, ArH), 8.21 (s, 1H, CH=N), 9.87 (s, 1H, NH),
4
,5-dihydrothiazol-2-yl)acetonitrile (16): Brown solid; yield 72%;
13
1
1
0.50 (s, 1H, NH); C NMR (600 MHz, DMSO-d ): δ 110.03 (1ArC),
6
-1
m.p. 257–258 ºC; IR (potassium bromide, cm ): 2942 (CH–), 2180
17.37 (1ArC), 121.55 (1ArC), 128.10 (1ArC), 128.21 (1ArC), 128.30
1
(
C≡N), 1719 (C=O), 1598 (C=N); H NMR (600 MHz, DMSO-d ): δ
6
(1ArC), 129.97 (2ArC), 130.49 (2ArC), 130.61 (2ArC), 130.74 (2ArC),
131.81 (2ArC), 132.84 (2ArC), 143.71 (1ArC), 144.31 (2ArC), 154.83
(C-6, triazine), 155.31 (C-5, triazine), 165.25 (C=N), 172.02 (C-3,
triazine), 172.31, 190.96 (2C=O). Anal. calcd for C H N O S : C,
3
.09 (s, 2H, CH ), 7.03–7.82 (m, 15H, ArH + CH–benzylidene). Anal.
2
calcd for C H N OS : C, 65.97; H, 3.49; N, 14.25; found: C, 65.84; H,
2
7
17
5
2
3
.41; N, 14.10%.
-(5-(4-[(5,6-Diphenyl-1,2,4-triazin-3-yl)thio]benzylidene)-
-oxothiazolidin-2-ylidene)-acetamide (17): Brown solid; yield
3
3
21
7
2 2
2
64.80; H, 3.46; N, 16.03; found: C, 64.72; H, 3.39; N, 15.92%.
4
Methyl 2-(2-(2-(4-[(5,6-diphenyl-1,2,4-triazin-3-yl)thio]benzylidene)-
hydrazinyl)-4-oxo-thiazol-5(4H)-ylidene)acetate (23): An equimolar
mixture of 4b (2.21 g, 5 mmol) and dimethyl acetylenedicarboxylate
(0.71 g, 5 mmol) in methanol (20 mL) was refluxed for 1 h. After
completion of the reaction, the reaction mixture was allowed to cool to
the room temperature. The solid thus separated was collected by filtration
and recrystallised using ethanol–DMF mixture. yellow solid; yield 72%;
-1
69%; m.p. 274–275 ºC; IR (potassium bromide, cm ): 3340, 3219,
1
3109 (NH /NH), 1656 (C=O), 1579 (C=N); H NMR (600 MHz,
2
DMSO-d ): δ 5.83 (s, 1H, methine-H), 6.76-7.72 (m, 16H, ArH + NH ),
6
2
8
.15 (s, 1H, CH–benzylidene), 10.25 (s, 1H, NH). Anal. calcd for
C H N O S : C, 63.64; H, 3.76; N, 13.74; found: C, 63.54; H, 3.69; N,
2
7
19
5
2 2
13.67%.
-1
Ethyl 2-(5-(4-[(5,6-diphenyl-1,2,4-triazin-3-yl)thio]benzylidene)-
m.p. 290–291ºC; IR (potassium bromide, cm ): 3172 (NH), 2953, 2756
1
4
-oxo-4,5-dihydro-thiazol-2-yl)acetate (18): Faint yellow solid; yield
(aliph. CH), 1730, 1699 (C=O), 1621 (C=N); H NMR (600 MHz,
-1
69%; m.p. 265–266 ºC; IR (potassium bromide, cm ): 3051 (CH-
DMSO-d ): δ 3.76 (s, 3H, OMe), 6.68 (s, 1H, CH=C), 7.23–7.83 (m,
6
1
13
arom), 2968 (CH–), 1712 (C=O), 1584 (C=N); H NMR (600 MHz,
14H, ArH), 8.43 (s, 1H, CH=N), 12.66 (s, 1H, NH); C NMR (600
CDCl ): δ 1.09 (t, 3H, CH ), 3.92 (s, 2H, CH ), 4.23 (q, 2H, CH ),
MHz, DMSO-d ): δ 56.38 (–OMe), 127.80 (1ArC), 128.06 (2ArC),
3
3
2
1
2
6
3
7.26–7.82 (m, 15H, ArH + CH–benzylidene). C NMR (150 MHz,
128.18 (1ArC), 128.22 (1ArC), 128.84 (2ArC), 129.05 (2ArC), 129.16