Synthesis and structure of novel 1,2,4-triazole derivatives containing the 2,4-dinitrophenylthio group

Article abstract of DOI:10.3184/030823409X401961

Some novel 1,2,4-triazole derivatives containing the 2,4-dinitrophenylthio group have been synthesised in high yields by means of the reactions of 3-substituted-4-amino -1H-1,2,4-triazole-5(4H)-thiones or (S-3-aryl-4- (benzylideneamino)-1H-l,2,4-triazole-5(4H)-thiones with 1-chloro-2,4- dinitrobenzene. The (S-3-aryl-4-(benzylideneamino)-1H-1,2,4-triazole-5(4H)- thiones were prepared by the reaction of 4-amino-3-aryl-2H-1,2,4-triazole-3(4H)- thiones and diverse aromatic aldehydes. The 2, 4-dinitrophenyl group linked to the S atom, not to the N atom, was confirmed by the crystal structures. The structures of all the compounds were determined by elemental analysis, IR, MS, ¹H NMR and ¹³C NMR.

Full text of DOI:10.3184/030823409X401961

114 RESEARCH PAPER
FEBRUARY, 114–119
JOURNAL OF CHEMICAL RESEARCH 2009
Synthesis and structure of novel 1,2,4-triazole derivatives containing the
2,4-dinitrophenylthio group
Qichun Dinga, Xinxiang Leia,b, Jianyu Jinc, Lixue Zhanga*, Huiai Dua and Haile Zhangd
aCollege of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325027, P.R. China
bChengdu Institute of Biology, Chinese Academy of Sciences, Chengdu 610041, P.R. China
cCollege of Education, Wenzhou University, Wenzhou 325027, P.R. China
dDepartment of Molecular Biology and Chemistry, Scripps Research Institute, San Diego, CA 92037, USA
Some novel 1,2,4-triazole derivatives containing the 2,4-dinitrophenylthio group have been synthesised in high yields by
means of the reactions of 3-substituted-4-amino -1H-1,2,4-triazole-5(4H)-thiones or (E)-3-aryl-4-(benzylideneamino)-1H-
1,2,4-triazole-5(4H)-thiones with 1-chloro-2,4-dinitrobenzene. The (E)-3-aryl-4-(benzylideneamino)-1H-1,2,4-triazole-5(4H)-
thiones were prepared by the reaction of 4-amino-3-aryl-2H-1,2,4-triazole-3(4H)-thiones and diverse aromatic aldehydes.
The 2, 4-dinitrophenyl group linked to the S atom, not to the N atom, was confirmed by the crystal structures. The
structures of all the compounds were determined by elemental analysis, IR, MS, 1H NMR and 13C NMR.
Keywords: 1,2,4-triazole, 1-chloro-2,4-dinitrobenzene, Schiff base, aromatic aldehydes, thioether
Various 1,2,4-triazole derivatives have been reported to possess
diverse types of biological properties such as antibacterial,1
antifungal,2,3 DQWLꢀLQÀDPPDWRU\ꢁ4 antihypertensive,5 antiviral,6
antileishmanial7 and antimigraine activities.8 They can be
used as plant-growth inhibitors,9 paints and surface active
agents,10 inhibitors of malignant cellular proliferation11 etc.
So the development of new compounds containing 1,2,4-
triazole rings is of much importance. On the other hand, 1,2,4-
triazole derivatives containing 2,4-dinitrophenylthio group
have been reported only by a few papers up to now and all
RIꢂWKHꢂUHSRUWHGꢂFRPSRXQGVꢂDUHꢂFRQ¿QHGꢂWRꢂꢃꢀDU\OꢂRUꢂꢃꢀDON\Oꢂ
1,2,4-triazoles.22-24
Several years ago Tang et al.25 made 2H-1,2,4-triazol-
3(4HꢄꢀRQHꢂ UHDFWꢂ ZLWKꢂ ꢅꢀÀXRURꢀꢆꢁꢃꢀGLQLWUREHQ]HQHꢁꢂ WKHQꢂ WKH\ꢂ
obtained
2-(2,4-dinitrophenyl)-2H-1,2,4-triazol-3(4H)-one
(Scheme 1) in which the 2,4-dinitrophenyl group was linked
to the N atom, but not to the O atom. There are also some
papers which have reported that the substituted groups linked
to the N atom of 3-substituted-4-amino-1H-1,2,4-triazol-
5(4H)-ones or (E)-4-(benzylideneamino)-5-aryl-1H-1,2,4-
triazol-5(4H)-ones, not to the O atom.26-32 As the substituted
groups linked to the O atom have not yet been reported,
we believed that when we made the sulfur analogues 3-
substituted-4-amino-1H-1,2,4-triazol-5(4H)-thiones or (E)-3-
aryl-4-(benzylideneamino)-1H-1,2,4-triazole-5(4H)-thiones
they would react with 1-chloro-2,4-dinitrobenzene in the
same way, the 2,4-dinitrophenyl group would be linked to
the N atom, not to the S atom in the products. But when we
obtained the crystal structures of 2e (Fig. 1) and 3b (Fig. 2),
ZHꢂZHUHꢂVXUSULVHGꢂWRꢂ¿QGꢂWKDWꢂWKHꢂꢆꢁꢃꢀGLQLWURSKHQ\OꢂJURXSꢂLVꢂ
linked to the S atom, not to the N atom (Scheme 2). Also to
our surprise, Sarva et al. made 4-amino-3-(4-propoxyphenyl)-
Fig. 1
1H-1,2,4-triazole-5(4H)-thione react with 1-(2-chloroethyl)-
4-(2-methoxyphenyl)piperazine in the solution of EtOH added
KOH and KI, when they got two products33(Scheme 5), and
Nasser also obtained two compounds when he made 4-amino-
3-(pyridin-2-yl)-1H-1,2,4-triazole-5(4H)-thione react with
(2S,3R,4R,5R,6R)-2-(acetoxymethyl)-6-bromotetrahydro-2H-
pyran-3,4,5-triyl triacetate34 (Scheme 6). Tang et al. made the
reaction in the alkalescent solution of NaHCO3 and EtOH,
while our reactions were carried out in the mixed solution of
Et3N and EtOH, which is also alkalescent, so we considered
that the conditions of the two methods were generally the
same. There are also thioethers obtained in several papers
in which 1,2,4-triazoles react with halohydrocarbons.24,35-37
NO2
O2N
O2N
NO2
F
N
NH
N
N
H
O
H
O
N
H
N
H
Scheme 1
* Correspondent. E-mail: zhanglixuelz@yahoo.com.cn

JOURNAL OF CHEMICAL RESEARCH 2009 115
O2N
N
N
R1
S
NO2
O2N
Cl
N
NH2
N
NH
NO2
R1
S
NO2
N
O2N
NH2
N
N
N
R1
S
R1: 2a: C H5-
2f: p-MeOC6H4-
2g: p-EtOC6H4-
2h: C6H5OCH2-
2i:o-OHC6H4-
2j: p-OHC6H4-
6
NH2
2b: m-MeC6H4-
2c: p-ClC6H4-
2d: p-MeC6H4-
2e: o-EtOC6H4-
Scheme 2
O2N
O2N
Cl
NO2
N
N
NH
N
S
NO2
S
HO
HO
N
N
NH2
NH2
2k
Scheme 3
Kulish et al. obtained 2-(5-(2,4-dinitrophenylthio)-4H-1,2,4-
triazol-3-yl)pyridine by the reaction of 3-(pyridin-2-yl)-1H-
1,2,4-triazole-5(4H)-thione and 1-chloro-2,4-dinitrobenzene
at the temperature of 2°C in alcohol (Scheme 4).24 That was
very interesting. Generally speaking, the nucleophilicity of
mercapto group is stronger than that of NH, so substituted
groups would be linked to the S rather than to N atom. At
the same time there are still many abnormal cases.33,34,38-41
As all of these points puzzled us, we decided to investigate the
mechanisms of these reactions. We now report the synthesis
RIꢂ WKHꢂ WLWOHꢂ FRPSRXQGVꢇꢂ 7KLVꢂ LVꢂ WKHꢂ ¿UVWꢂ UHSRUWꢂ RIꢂ WKHꢂ ꢆꢁꢃꢀ
dinitrophenyl group linking to the S atom of 3-substituted-
4-amino-1H-1,2,4-triazole-5(4H)-thiones and (E)-3-aryl-4-
(benzylideneamino)-1H-1,2,4-triazole-5(4H)-thiones.
O2N
O2N
N
N
N
NH
Cl
NO2
N
N
S
NO2
S
N
H
N
H
Scheme 4
N
N
Cl
O
O
N
NH
O
N
S
KOH and KI
N
N
NH2
O
N
N
N
N
O
O
S
+
N
N
S
N
N
NH2
NH2
58%
28%
Scheme 5

116 JOURNAL OF CHEMICAL RESEARCH 2009
Br
AcO
N
NH
N
R
O
R
S
Et N and DMF
3
S
+
OAc
R
R
N
AcO
AcO
NH2
OAc
OAc
AcO
R
R
O
S
R
R
OAc
N
N
N
O
R
R
S
N
N
S
N
S
OAc
OAc
+
N
R
S
N
NH2
AcO
OAc
NH2
Scheme 6
EtOH
NH2NH2
KOH
CS2
R1CONHNH2
R1CONHNHCS2 K+
-
R1COOEt
R1COOH
NH2NH2
N
NH
N
N
R1
R1
SH
S
N
N
NH2
NH2
1
Scheme 7
4-Amino-3-aryl-1H-1,2,4-triazole-5(4H)-thiones, whose taut-
omers are 4-amino-3-aryl-5-mercapto-1,2,4-triazoles, are
generally prepared from aromatic acids (Scheme 7), following
the procedure of Zhang et al. 42
Experimental
Carbon, hydrogen and nitrogen analyses were determined on a
Flash-1112 series elemental analyser. IR spectra were recorded on a
We made 1 react with 1-chloro-2,4-dinitrobenzene in
the mixed solution of Et3N and EtOH at the temperature
of 120°&ꢁꢂ UHÀX[LQJꢂ IRUꢂ RQO\ꢂ DERXWꢂ ꢅꢈꢂ PLQꢇꢂ ,Qꢂ WKLVꢂ ZD\ꢁꢂ
we obtained 3-(2,4-dinitrophenylthio)-5-aryl-4H-1,2,4-triazol-
4-amines readily (Scheme 2). We also used 4-amino-5-
(3-hydroxypropyl)-2H-1,2,4-triazole-3(4H)-thione which was
prepared following the procedure of Zhang et al. 43 (Scheme 8)
to react with 1-chloro-2,4-dinitrobenzene in the same
conditions as mentioned above. We obtained 3-(4-amino-5-
(2,4-dinitrophenylthio)-4H-1,2,4-triazol-3-yl)propan-1-ol
successfully (Scheme 3).
Meanwhile, we used (E)-3-aryl-4-(benzylideneamino)-1H-
1,2,4-triazole-5(4H)-thiones (2) that were prepared by the
reaction of 4-amino-3-aryl-1H-1,2,4-triazole-5(4H)-thiones
and diverse aromatic aldehydes to react with 1-chloro-2,4-
dinitrobenzene in the same condition as mentioned above.
In this way, we successfully obtained (E)-N-benzylidene-3-
(2,4-dinitrophenylthio)-5-aryl-4H-1,2,4-triazol-4-amines (3,
Scheme 9) and the crystal structure of 3b is shown in Fig. 2.
Fig. 2
O
S
N
NH
H2N
NH 2
N
H
N
H
HO
S
O
N
NH2
Scheme 8

JOURNAL OF CHEMICAL RESEARCH 2009 117
N
N
R1
S
NO 2
N
N
O2N
O2N
R 2
N
NH
N
NH
Cl
S
NO2
R2CHO
3
R1
S
R1
N
NO 2
N
N
O2N
NH2
R2
2
1
N
N
R1
S
N
N
R2
3
3a: R1 = p-EtOC6H4- R2 = p-FC6H4-
3f: R1 =p-MeOC6H4- R2 =p-BrC6H4-
3g: R1 = p-HOC6H4- R2 = m-NO2C6H4-
3b: R1 = p-MeOC6H4- R2 = p-(CH3)2NC6H4-
3c: R1 = o-EtOC6H4- R2 = p-MeC6H4-
3h: R1 = C6H5-
3i: R1 = C6H5-
R2 = p-HOC6H4-
R2 = o-HOC6H4-
3d: R1 = o-HOC6H4-
3e: R1 = p-ClC6H4-
R2 = o-FC6H4-
R2= p-MeOC6H4-
Scheme 9
Nicolet 670FT-IR using the smart OMNI-Sampler in the range 4000–
400 cm-1. MS spectra were recorded on an Agilent 1100 LC/MS.
1H NMR and 13C NMR spectra were recorded on a Bruker Avance-
300 NMR Spectrometer in DMSO-d6 solution using TMS as an
internal reference. Melting points were determined on an XT-4
melting point apparatus and were uncorrected. The crystal structures
were measured on Bruker APEX area-detector diffractometer.
All chemicals and solvents used were of AR grade.
(C=N), 1469 (aryl skeleton), 702 (C–S–C); MS-ESI (m/z): 373.6
(M+ + 1); 1H NMR (300 MHz, DMSO-d6, 25°C, TMS) G (ppm) =
8.93 (d, J = 2.6 Hz, 1H, ArH), 8.44–8.40 (m, 1H, ArH), 7.92–7.83
(m, 2H, ArH), 7.47–7.42 (m, 2H, ArH), 7.17 (d, J = 8.9 Hz, 1H, ArH),
6.25 (s, 2H, NH2), 2.38 (s, 3H, CH3); 13C NMR (DMSO-d6) G (ppm)
= 156.37, 147.25, 146.03, 141.96, 138.34, 137.71, 129.76, 128.80,
128.62, 128.41, 127.65, 126.90, 125.30, 123.54, 20.68; Elemental
anal. Calcd for C15H12N6O4S: C 48.38, H 3.25, N 22.57. Found: C
48.56, H 3.30, N 22.38%.
3-(4-Chlorophenyl)-5-(2,4-dinitrophenylthio)-4H-1,2,4-triazol-
4-amine (2c): M.p. 90–92°C; yield: 92.4%; IR (cm-1): 3086 (ArH),
1586 (C=N), 1475 (aryl skeleton), 698 (C–S–C); MS-ESI (m/z):
393.3 (M+ + 1); 1H NMR (300 MHz, DMSO-d6, 25°C, TMS)
G (ppm) = 8.94 (d, J = 2.6 Hz, 1H, ArH), 7.78 (dd, J1 = 3.6 Hz,
J2 = 8.5 Hz, 2H, ArH), 7.57 (dd, J1 = 1.8 Hz, J2 = 7.5 Hz, 1H, ArH),
7.18 (dd, J1 = 2.3 Hz, J2 = 7.6 Hz, 1H, ArH), 6.35 (d, J = 8.5 Hz, 2H,
ArH), 6.13 (s, 2H, NH2); 13C NMR (DMSO-d6) G (ppm) = 154.28,
148.68, 147.18, 145.24, 135.20, 137.14, 129.77, 129.58, 128.86,
128.23, 127.90, 125.34; Elemental anal. Calcd for C14H9ClN6O4S:
C 42.81, H 2.31, N 21.40. Found: C 42.98, H 2.36, N 21.22%.
3-(2,4-Dinitrophenylthio)-5-p-tolyl-4H-1,2,4-triazol-4-amine (2d):
M.p. 266–268°C; yield: 89.2%; IR (cm-1): 3093 (ArH), 1564 (C=N),
1465 (aryl skeleton), 701 (C–S–C); MS-ESI (m/z): 373.4 (M+ + 1);
1H NMR (300 MHz, DMSO-d6, 25°C, TMS) G (ppm) = 8.93 (d,
J = 2.3 Hz, 1H, ArH), 8.44 (dd, J1 = 2.6 Hz, J2 = 8.3 Hz, 2H, ArH),
7.68 (dd, J1 = 1.9 Hz, J2 = 7.9 Hz, 1H, ArH), 7.12 (dd, J1 = 2.2 Hz,
J2 = 8.9 Hz, 1H, ArH), 6.67 (d, J = 8.5 Hz, 2H, ArH), 6.17 (s, 2H,
NH2), 2.35 (s, 3H, CH3); 13C NMR (DMSO-d6) G (ppm) = 155.79,
150.55, 145.43, 145.12, 144.52, 142.01, 129.75, 129.10, 128.19,
121.11, 113.45, 113.20, 21.2; Elemental anal. Calcd for C15H12N6O4S:
C 48.38, H 3.25, N 22.57. Found: C 48.17, H 3.31, N 22.76%.
3-(2,4-Dinitrophenylthio)-5-(2-ethoxyphenyl)-4H-1,2,4-triazol-4-
amine (2e): M.p. 168–170°C; yield: 90.8%; IR (cm-1): 3099 (ArH),
1595 (C=N), 1462 (aryl skeleton), 917 (C–S–C); MS-ESI (m/z): 403.2
(M+ + 1); 1H NMR (300 MHz, DMSO-d6, 25°C, TMS) G (ppm) = 8.97
(d, J = 2.3 Hz, 1H, ArH), 8.47–8.43 (m, 1H, ArH), 7.61–7.51 (m, 2H,
ArH), 7.23–7.01 (m, 3H, ArH), 5.85 (s, 2H, NH2), 4.12 (q, J = 6.8 Hz,
2H, CH2), 1.25 (t, J = 6.8 Hz, 3H, CH3); 13C NMR (DMSO-d6) G
(ppm) = 156.38, 156.07, 145.90, 145.30, 144.55, 142.13, 132.58,
131.64, 129.34, 128.53, 121.68, 120.69, 115.53, 112.61, 64.08, 14.54;
Elemental anal. Calcd for C16H14N6O5S: C 47.76, H 3.51, N 20.89.
Found: C 47.98, H 3.45, N 20.62%.
Synthesis of 3-(2,4-dinitrophenylthio)-5-substituted-4H-1,2,4-triazol-
4-amine (2a–k): general procedure
A mixture of 4-amino-3-substituted-1H-1,2,4-triazole-5(4H)-thione
(0.02 mol, 1), and 1-chloro-2,4-dinitrobenzene (0.02 mol) were
added EtOH (10 mL) and Et31ꢂꢉꢊꢈꢂP/ꢄꢁꢂUHÀX[HGꢂDWꢂWKHꢂWHPSHUDWXUHꢂ
of 120°C (on the oil-bath) for only about 10 min. After concentration
under reduced pressure, the crude products were recrystallised from
alcohol to afford the compounds (2a–k).
Synthesis of (E)-3-(2,4-dinitrophenylthio)-N-(4-benzylidene)-5-aryl-
4H-1,2,4-triazol-4-amines (3a–i): general procedure
Aromatic aldehydes (0.02 mol, distilled under reduced pressure
before use) were added to a solution of 4-amino-3-substituted-1H-
1,2,4-triazole-5-thione (0.02 mol) in absolute ethanol (30 mL).
The pH value then was adjusted to 5–6 with dilute HCl.
7KHꢂ PL[WXUHꢂ ZDVꢂ VWLUUHGꢂ DQGꢂ UHÀX[HGꢂ IRUꢂ DERXWꢂ ꢆꢂ Kꢇꢂ 7KHꢂ FUXGHꢂ
products were recrystallised from ethanol and gave the pure (E)-
3-aryl-4-(benzylidene-amino)-1H-1,2,4-triazole-5(4H)-thiones (2).
Then to a solution of 2 (0.02 mol) dissolved in EtOH (10 mL) and
Et3N (30 mL) was added 1-chloro-2,4-dinitrobenzene (0.02 mol).
7KHꢂPL[WXUHꢂZDVꢂUHÀX[HGꢂIRUꢂRQO\ꢂDERXWꢂꢅꢈꢂPLQXWHVꢂXQGHUꢂVWLUULQJꢂDWꢂ
the temperature of 120°C (on the oil-bath). After concentration under
reduced pressure, the crude products were recrystallised from alcohol
to afford the compounds (3a–i).
3-(2,4-Dinitrophenylthio)-5-phenyl-4H-1,2,4-triazol-4-amine (2a):
M.p. 246–248°C; yield: 92.6%; IR (cm-1): 3104 (ArH), 1598 (C=N),
1463 (aryl skeleton), 703 (C–S–C); MS-ESI (m/z): 359.4 (M+ + 1);
1H NMR (300 MHz, DMSO-d6, 25°C, TMS) G (ppm) = 8.95 (d,
J = 2.5 Hz, 1H, ArH), 8.44–8.40 (m, 1H, ArH), 8.16–8.13 (m, 2H,
ArH), 7.62–7.56 (m, 3H, ArH), 7.18 (d, J = 8.9 Hz, 1H, ArH), 6.31 (s,
2H, NH2); 13C NMR (DMSO-d6) G (ppm) = 155.24, 146.87, 145.22,
144.63, 141.44, 130.16, 129.87, 128.44, 128.26, 128.09, 126.49,
121.14; Elemental anal. Calcd for C14H10N6O4S: C 46.93,H 2.81,
N 23.45. Found: C 46.72, H 2.86, N 23.56%.
3-(2,4-Dinitrophenylthio)-5-(4-methoxyphenyl)-4H-1,2,4-triazol-
4-amine (2f): M.p. 248–250°C; yield: 91.2%; IR (cm-1): 3096 (ArH),
1598 (C=N), 1461 (aryl skeleton), 684 (C–S–C); MS-ESI (m/z):
3-(2,4-Dinitrophenylthio)-5-m-tolyl-4H-1,2,4-triazol-4-amine
(2b): M.p. 88–90°C; yield: 91.3%; IR (cm-1): 3100 (ArH), 1598

118 JOURNAL OF CHEMICAL RESEARCH 2009
389.6 (M+ + 1); 1H NMR (300 MHz, DMSO-d6, 25°C, TMS) G (ppm)
= 8.94 (d, J = 2.4 Hz, 1H, ArH), 8.44–8.40 (m, 1H, ArH), 7.86 (dd,
J1 = 2.3 Hz, J2 = 8.5 Hz, 2H, ArH), 7.12 (d, J = 8.9 Hz, 1H, ArH),
6.66 (dd, J1 = 3.6 Hz, J = 7.8 Hz, 2H, ArH), 6.15 (s, 2H, NH2), 3.73 (s,
3H, CH3); 13C NMR (DMSO-d6) G (ppm) = 160.54, 155.78, 150.63,
145.41, 145.10, 144.50, 142.05, 129.74, 129.09, 128.22, 121.15,
113.12, 55.8; Elemental anal. Calcd for C15H12N6O5S: C 46.39,
H 3.11, N 21.64. Found: C 46.15, H 3.15, N 21.84%.
3-(2,4-Dinitrophenylthio)-5-(4-ethoxyphenyl)-4H-1,2,4-triazol-4-
amine (2g): M.p. 121–123°C; yield: 88.9%; IR (cm-1): 3093 (ArH),
1588 (C=N), 1477 (aryl skeleton), 699 (C–S–C); MS-ESI (m/z):
403.4 (M+ + 1); 1H NMR (300 MHz, DMSO-d6, 25°C, TMS) G (ppm)
= 8.94 (d, J = 2.3 Hz, 1H, ArH), 8.43–8.37 (m, 1H, ArH), 8.08 (dd,
J1 = 2.0 Hz, J2 = 7.9 Hz, 2H, ArH), 7.91 (d, J = 8.6 Hz, 1H, ArH), 7.10
(dd, J1 = 3.2 Hz, J = 8.9 Hz, 2H, ArH), 6.25 (s, 2H, NH2), 4.10 (q,
J = 7.6 Hz, 2H, CH2), 1.34 (t, J = 7.6 Hz, 3H, CH3); 13C NMR
(DMSO-d6) G (ppm) = 160.02, 155.08, 146.28, 145.20, 144.62,
141.64, 129.86, 128.45, 121.12, 118.76, 114.84, 114.44, 63.31, 14.43;
Elemental anal. Calcd for C16H14N6O5S: C 47.76, H 3.51, N 20.89.
Found: C 47.98, H 3.44, N 20.65%.
3-(2,4-Dinitrophenylthio)-5-(phenoxymethyl)-4H-1,2,4-triazol-4-
amine (2h): M.p. 190–192°C; yield: 92.6%; IR (cm-1): 3096 (ArH),
1594 (C=N), 1481 (aryl skeleton), 702 (C–S–C); MS-ESI (m/z): 389.3
(M+ + 1); 1H NMR (300 MHz, DMSO-d6, 25°C, TMS) G (ppm) = 8.96
(d, J = 2.5 Hz, 1H, ArH), 8.47–8.43 (m, 1H, ArH), 7.37–7.32 (m, 2H,
ArH), 7.12–7.08 (m, 3H, ArH), 7.03–6.99 (m, 1H, ArH), 6.24 (s, 2H,
NH2), 5.31 (s, 2H, CH2); 13C NMR (DMSO-d6) G (ppm) = 158.01,
154.23, 145.41, 141.48, 135.42, 129.85, 129.72, 128.47, 128.20,
121.57, 121.17, 115.09, 59.38; Elemental anal. Calcd for C15H12N6O5S:
C 46.39, H 3.11, N 21.64. Found: C 46.24, H 3.17, N 21.71%.
2-(4-Amino-5-(2,4-dinitrophenylthio)-4H-1,2,4-triazol-3-yl)
phenol (2i): M.p. 257–259°C; yield: 89.7%; IR (cm-1): 3426 (OH),
3095 (ArH), 1585 (C=N), 1465 (aryl skeleton), 681 (C–S–C); MS-ESI
(m/z): 375.4 (M+ + 1); 1H NMR (300 MHz, DMSO-d6, 25°C, TMS) G
(ppm) = 10.53 (s, 1H, OH), 8.79 (d, J = 2.3 Hz, 1H, ArH), 8.48–8.45
(m, 1H, ArH), 8.10 (d, J = 2.5 Hz, 1H, ArH), 7.67 (d, J = 8.9 Hz,
1H, ArH), 7.58 (d, J = 7.6 Hz, 1H, ArH), 7.37–7.34 (m, 1H, ArH),
6.96–6.94 (m, 1H, ArH), 6.18 (s, 2H, NH2); 13C NMR (DMSO-d6)
G (ppm) = 156.51, 155.70, 147.20, 146.09, 133.29, 131.45, 130.99,
130.23, 128.84, 123.05, 121.51, 119.82, 116.77, 112.03; Elemental
anal. Calcd for C14H10N6O5S: C 44.92, H 2.69, N 22.45. Found: C
45.08, H 2.73, N 22.26.
(E)-N-(4-(Dimethylamino)benzylidene)-3-(2,4-dinitrophenylthio)-
5-(4-methoxyphenyl)-4H-1,2,4-triazol-4-amine(3b):M.p.223–225°C;
yield: 89.7%; IR (cm-1): 3097 (ArH), 1605 (C=N), 1478 (aryl skeleton),
708 (C–S–C); MS-ESI (m/z): 520.2 (M+ + 1); 1H NMR (300 MHz,
DMSO-d6, 25°C, TMS) G (ppm) = 8.85 (s, 1H, ArH), 8.66 (s, 1H,
N=CH), 8.44 (d, J = 8.7 Hz, 2H, ArH), 7.94 (dd, J1 = 1.6, J2 = 7.9 Hz,
2H, ArH), 7.55 (dd, J1 = 3.5 Hz, J2 = 8.0 Hz, 2H, ArH), 7.09 (dd, J1
= 2.7, J2 = 8.4 Hz, 2H, ArH), 6.74 (dd, J1 = 1.8 Hz, J2 = 8.4 Hz, 2H,
ArH), 3.80 (s, 3H, OCH3), 3.01 (s, 6H, NCH3); 13C NMR (DMSO-d6)
G (ppm) = 170.65, 160.91, 153.88, 152.28, 145.46, 144.29, 141.27,
131.23, 129.90, 129.63, 128.80, 124.30, 121.64, 118.64, 117.74,
114.48, 111.75, 55.51, 40.46; Elemental anal. Calcd for C24H21N7O5S:
C 55.48, H 4.07, N 18.87. Found: C 55.30, H 4.12, N 18.99%.
(E)-3-(2,4-Dinitrophenylthio)-5-(2-ethoxyphenyl)-N-(4-methyl-
benzylidene)-4H-1,2,4-triazol-4-amine (3c): M.p. 87–89°C; yield:
92.5%; IR (cm-1): 3093 (ArH), 1608 (C=N), 1481 (aryl skeleton),
702 (C–S–C); MS-ESI (m/z): 505.5 (M+ + 1); 1H NMR (300 MHz,
DMSO-d6, 25°C, TMS) G (ppm) = 8.90 (s, 1H, ArH), 8.56 (s, 1H,
N=CH), 8.46 (dd, J1 = 2.6 Hz, J2 = 8.8 Hz, 1H, ArH), 7.68 (dd,
J1 = 1.8 Hz, J2 = 7.3 Hz, 1H, ArH), 7.57-7.52 (m, 1H, ArH), 7.44 (dd,
J1 = 3.8 Hz, J2 = 7.8 Hz, 2H, ArH), 7.25–7.10 (m, 5H, ArH), 3.86
(q, J = 6.8 Hz, 2H, CH2), 2.30 (s, 3H, CH3), 1.11 (t, J = 6.8 Hz, 3H,
CH3); 13C NMR (DMSO-d6) G (ppm) = 167.30, 155.69, 151.25,
145.49, 144.44, 144.09, 141.93, 141.20, 132.98, 132.00, 130.03,
129.52, 128.82, 128.65, 121.73, 120.86, 115.03, 112.53, 63.77, 21.39,
14.47; Elemental anal. Calcd for C24H20N6O5S: C 57.14, H 4.00,
N 16.66. Found: C 57.32, H 4.03, N 16.52%.
(E)-2-(5-(2,4-Dinitrophenylthio)-4-(2-fluorobenzylideneamino)-
4H-1,2,4-triazol-3-yl)phenol (3d): M.p. 202–204°C; yield: 89.6%;
IR (cm-1): 3431 (OH), 3101 (ArH), 1598 (C=N), 1478 (aryl skeleton),
698 (C–S–C); MS-ESI (m/z): 479.4 (M - 1); 1H NMR (300 MHz,
DMSO-d6, 25°C, TMS) G (ppm) = 10.03 (s, 1H, OH), 8.90 (d, J = 8.2 Hz,
1H, ArH), 8.60 (s, 1H, N=CH), 8.39 (d, J = 3.7 Hz, 1H, ArH),
7.94 (d, J = 8.4 Hz, 1H, ArH), 7.41 (d, J = 4.7 Hz, 1H, ArH), 7.34
(d, J = 8.0 Hz, 2H, ArH), 7.03–6.90 (m, 5H, ArH); 13C NMR (DMSO-d6)
G (ppm) = 163.47, 161.80, 160.11, 157.01, 156.33, 148.71, 134.99, 132.58,
131.91, 131.34, 127.37, 125.44, 121.47, 120.01, 119.56, 119.07, 116.71,
116.44, 116.13, 112.94, 112.86; Elemental anal. Calcd for C21H13FN6O5S:
C 52.50, H 2.73, N 17.49. Found: C 52.75, H 2.68, N 17.61%.
(E)-3-(4-Chlorophenyl)-5-(2,4-dinitrophenylthio)-N-(4-methoxy-
benzylidene)-4H-1,2,4-triazol-4-amine (3e): M.p. 102–104°C; yield:
91.8%; IR (cm-1): 3096 (ArH), 1622 (C=N), 1483 (aryl skeleton),
708 (C–S–C); MS-ESI (m/z): 511.4 (M+ + 1); 1H NMR (300 MHz,
DMSO-d6, 25°C, TMS) G (ppm) = 8.95 (s, 1H, ArH), 8.62 (s,
1H, N=CH), 8.43 (d, J = 8.7 Hz, 1H, ArH), 7.99 (dd, J1 = 2.4 Hz,
J2 = 8.5 Hz, 2H, ArH), 7.76 (dd, J1 = 4.2 Hz, J2 = 8.6 Hz, 2H, ArH), 7.66
(dd, J1 = 3.6 Hz, J2 = 8.6 Hz, 2H, ArH),7.59 (d, J = 8.6 Hz, 1H, ArH), 7.06
(dd, J1 = 1.8 Hz, J2 = 8.6 Hz, 2H, ArH), 3.85 (s, 3H, OCH3); 13C NMR
(DMSO-d6) G (ppm) = 170.84, 163.25, 151.76, 148.65, 145.56, 144.33,
140.63, 135.63, 131.65, 131.05, 129.22, 129.03, 128.20, 124.83, 123.45,
121.62, 114.89; Elemental anal. Calcd for C22H15ClN6O5S: C 51.72, H
2.96, N 16.45. Found: C 51.56, H 3.00, N 16.54%.
4-(4-Amino-5-(2,4-dinitrophenylthio)-4H-1,2,4-triazol-3-yl)
phenol (2j): M.p. 258–260°C; yield: 92.4%; IR (cm-1): 3426 (OH),
3096 (ArH), 1592 (C=N), 1471 (aryl skeleton), 692 (C–S–C);
MS-ESI (m/z): 375.2 (M+ + 1); 1H NMR (300 MHz, DMSO-d6,
25°C,TMS) G (ppm) = 10.01 (s, 1H, OH), 8.95 (d, J = 2.3 Hz, 1H,ArH),
8.41 (dd, J1 = 1.8 Hz, J2 = 8.2 Hz, 1H, ArH), 8.01 (dd, J1 = 3.5 Hz,
J2=8.5Hz,1H,ArH),7.16(d,J=8.9Hz,2H,ArH),6.93(dd,J1=2.4Hz,
J2 = 8.4 Hz, 2H, ArH), 6.22 (s, 2H, NH2); 13C NMR (DMSO-d6)
G (ppm) = 159.71, 155.83, 146.56, 145.58, 144.94, 142.37, 131.06,
130.20, 128.82, 120.41, 117.71, 115.76; Elemental anal. Calcd for
C14H10N6O5S: C 44.92, H 2.69, N 22.45. Found: C 44.75, H 2.74,
N 22.64%.
(E)-N-(4-Bromobenzylidene)-3-(2,4-dinitrophenylthio)-5-(4-methoxy-
phenyl)-4H-1,2,4-triazol-4-amine (3f): M.p. 242–244°C; yield: 93.8%;
IR (cm-1): 3092 (ArH), 1614 (C=N), 1465 (aryl skeleton), 693 (C–S–
3-(4-Amino-5-(2,4-dinitrophenylthio)-4H-1,2,4-triazol-3-yl)
propan-1-ol (2k): M.p. 147–149°C; yield: 93.6%; IR (cm-1): 3428
(OH), 3094 (ArH), 2950 (CH2), 1592 (C=N), 1463 (aryl skeleton),
1
C); MS-ESI (m/z): 555.4 (M+ + 1); H NMR (300 MHz, DMSO-d6,
25°C, TMS) G (ppm) = 9.02 (s, 1H, ArH), 8.63 (s, 1H, N=CH), 8.44
(d, J = 8.9 Hz, 2H, ArH), 7.83 (dd, J1 = 2.8 Hz, J2 = 7.9 Hz, 1H, ArH),
7.72 (dd, J1 = 3.6 Hz, J2 = 8.4 Hz, 3H, ArH), 7.06 (dd, J1 = 4.2 Hz,
J2 = 8.7 Hz, 4H, ArH), 3.81 (s, 3H, OCH3); 13C NMR (DMSO-d6)
G (ppm) = 161.13, 152.53, 146.83, 144.40, 140.89, 138.79, 132.65,
131.39, 131.07, 130.63, 129.94, 129.88, 128.80, 127.79, 124.40, 120.09,
114.15, 55.53; Elemental anal. Calcd for C22H15BrN6O5S: C 47.58,
H 2.72, N 15.13. Found: C 47.70, H 2.75, N 15.02%.
1
691 (C–S–C); MS-ESI (m/z): 341.2 (M+ + 1); H NMR (300 MHz,
DMSO-d6, 25°C, TMS) G (ppm) = 8.90 (d, J = 2.4 Hz, 1H, ArH),
8.39–8.35 (m, 1H, ArH), 6.99 (d, J = 8.9 Hz, 1H, ArH), 5.96 (s,
2H, NH2), 4.56 (s, 1H, OH), 3.47 (t, J = 7.9 Hz, 2H, CH2), 2.82 (t,
J = 8.9 Hz, 2H, CH2), 1.91–1.82 (m, 2H, CH2); 13C NMR (DMSO-d6)
G (ppm) = 158.65, 145.24, 144.90, 144.51, 142.21, 129.69, 128.45,
121.48, 60.22, 29.58, 21.31; Elemental anal. Calcd for C11H12N6O5S:
C 38.82, H 3.55, N 24.69. Found: C 38.98, H 3.58, N 24.58%.
(E)-3-(2,4-Dinitrophenylthio)-5-(4-ethoxyphenyl)-N-(4-fluoro-
benzylidene)-4H-1,2,4-triazol-4-amine (3a): M.p. 131–133°C; yield:
91.8%; IR (cm-1): 3100 (ArH), 1600 (C=N), 1470 (aryl skeleton), 692
(C–S–C); MS-ESI (m/z): 509.1 (M+ + 1); 1H NMR (300 MHz, DMSO-
d6, 25°C, TMS) G (ppm) = 8.98 (s, 1H, ArH), 8.64 (s, 1H, N=CH), 8.44
(d, J = 8.7 Hz, 1H, ArH), 7.95 (dd, J1 = 3.5 Hz, J2 = 7.8 Hz, 2H, ArH),
7.42 (dd, J1 = 2.5 Hz, J2 = 8.7 Hz, 2H, ArH), 7.36 (dd, J1 = 1.8 Hz,
J2 =8.9Hz,2H,ArH),7.33(d,J=8.4Hz,1H,ArH),7.03(dd,J1 =1.6Hz,
J2 = 7.9 Hz, 2H, ArH), 4.05 (q, J = 8.6 Hz, 2H, OCH2), 1.33 (t,
J = 8.6 Hz, 3H, CH3); 13C NMR (DMSO-d6) G (ppm) = 165.26,
160.26, 152.14, 148.45, 147.36, 145.47, 143.32, 137.11, 135.18,
133.36, 132.48, 131.14, 129.74,127.90, 120.90, 114.81,113.22, 63.35,
14.39; Elemental anal. Calcd for C23H17FN6O5S: C 54.33, H 3.37, N
16.53. Found: C 54.15, H 3.33, N 16.70%.
(E)-4-(5-(2,4-Dinitrophenylthio)-4-(3-nitrobenzylideneamino)-
4H-1,2,4-triazol-3-yl)phenol (3g): M.p. 238–240°C; yield: 91.7%;
IR (cm-1): 3426 (OH), 3098 (ArH), 1592 (C=N), 1462 (aryl skeleton),
696 (C–S–C); MS-ESI (m/z): 508.5 (M+ + 1); 1H NMR (300 MHz,
DMSO-d6, 25°C, TMS) G (ppm) = 10.20 (s, 1H, OH), 8.95 (s, 1H,
ArH), 8.63 (s, 1H, N=CH), 8.48–8.43 (m, 4H, ArH), 8.22 (d, J = 7.1 Hz,
1H, ArH), 8.13 (dd, J1 = 2.7 Hz, J2 = 8.9 Hz, 1H, ArH), 7.80 (dd,
J1 = 1.9 Hz, J2 = 7.7 Hz, 1H, ArH), 7.13 (d, J = 9.2 Hz, 1H, ArH), 6.93
(dd, J1 = 2.8 Hz, J2 = 7.6 Hz, 2H, ArH); 13C NMR (DMSO-d6) G (ppm)
= 168.79, 159.81, 153.01, 148.33, 145.55, 144.45, 140.91, 135.01,
132.77, 131.30, 130.23, 129.86, 128.85, 127.88, 123.68, 121.61,
120.34, 116.46, 115.91; Elemental anal. Calcd for C21H13N7O7S:
C 49.71, H 2.58, N 19.32. Found: C 49.62, H 2.61, N 19.43%.
(E)-4-((3-(2,4-Dinitrophenylthio)-5-phenyl-4H-1,2,4-triazol-4-ylimino)
methyl)phenol (3h): M.p. 136–138°C; yield: 93.8%; IR (cm-1):

JOURNAL OF CHEMICAL RESEARCH 2009 119
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3438 (OH), 3102 (ArH), 1596 (C=N), 1454 (aryl skeleton), 698
(C–S–C); MS-ESI (m/z): 463.0 (M+ + 1); 1H NMR (300 MHz, DMSO-
d6, 25°C, TMS) G (ppm) = 10.02 (s, 1H, ArOH), 8.86 (d, J = 2.2 Hz, 1H,
ArH), 8.68(s, 1H, N=CH), 8.44–8.41(m, 1H,ArH), 7.97(dd, J1 =3.5Hz,
J2 = 8.4 Hz, 2H, ArH), 7.62–7.54 (m, 5H, ArH), 7.19 (d, J = 8.9 Hz,
1H, ArH), 6.86 (dd, J1 = 2.2 Hz, J2 = 8.5 Hz, 2H, ArH); 13C NMR
(DMSO-d6) G (ppm) = 171.23, 163.23, 152.74, 145.87, 144.78, 141.99,
141.05, 132.06, 130.93, 130.32, 129.31, 128.61, 128.05, 126.46,
122.40, 121.86, 116.69; Elemental anal. Calcd for C21H14N6O5S: C
54.54, H 3.05, N 18.17. Found: C 54.42, H 3.08, N 18.25%.
(E)-2-((3-(2,4-Dinitrophenylthio)-5-phenyl-4H-1,2,4-triazol-4-
ylimino)methyl)phenol (3i):M.p. 98–100°C; yield: 89.3%; IR (cm-1):
3427 (OH), 3099 (ArH), 1596 (C=N), 1458 (aryl skeleton), 698
(C–S–C); MS-ESI (m/z): 463.4 (M+ + 1); 1H NMR (300 MHz,
DMSO-d6, 25°C, TMS) G (ppm) = 10.08 (s, 1H, ArOH), 8.97 (s, 1H,
ArH), 8.67 (s, 1H, N=CH), 8.45 (d, J = 2.7 Hz, 1H, ArH), 8.17–8.14
(m, 1H, ArH), 7.98 (d, J = 8.5 Hz, 2H, ArH), 7.79 (d, J = 8.7 Hz, 3H,
ArH), 7.31 (d, J = 8.7 Hz, 2H, ArH), 6.88 (d, J = 8.2 Hz, 2H, ArH);
13C NMR (DMSO-d6) G (ppm) = 166.69, 159.36, 155.74, 152.93,
149.15, 145.61, 137.85, 130.73, 129.29, 128.99, 128.45, 127.56,
126.94, 121.90, 121.72, 121.43, 120.17, 117.86, 117.10; Elemental
anal. Calcd for C21H14N6O5S: C 54.54, H 3.05, N 18.17. Found:
C 54. 68, H 3.01, N 18.02%.
:Hꢂ DUHꢂ JUDWHIXOꢂ IRUꢂ ¿QDQFLDOꢂ VXSSRUWꢂ IURPꢂ WKHꢂ 1DWXUDOꢂ
6FLHQFHꢂ)RXQGDWLRQꢂRIꢂ=KHMLDQJꢂ3URYLQFHꢁꢂ&KLQDꢂꢉ3URMHFWꢂ1Rꢇꢂ
M203149).
Received 26 October 2008; accepted 10 December 2008
Paper 08/0263 doi:10.3184/030823409X401961
Published online: 18 February 2009
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