Synthesis and insecticidal activity of tetrazole-linked triazole derivatives

Article abstract of DOI:10.1002/jhet.2078

A new series of 4-(4-substitutedbenzylideneamino)-5-((1-methyl-1H-tetrazol-5-ylthio)methyl)-4H-1,2,4-triazole-3-thiol derivatives (5a, 5b, 5c, 5d, 5e, 5f, 5g, 5h, 5i, 5j, 5k) are prepared using 4-amino-5-((1-methyl-1H-tetrazol-5-ylthio)methyl-4H-1,2,4-triazole-3-thiol (4), as an intermediate compound. The structures of all the newly synthesized products are established supported by their spectral ¹H NMR, ¹³C NMR, FTIR, electrospray ionization mass spectrometry (mass), and analytical data. All the compounds are screened for their insecticidal activity against Plodia interpunctella, and six compounds exhibited significant activity.

Full text of DOI:10.1002/jhet.2078

Month 2014
Synthesis and Insecticidal Activity of Tetrazole-Linked Triazole
Derivatives
*
Suresh Maddila, Ramakanth Pagadala and Sreekanth B. Jonnalagadda
School of Chemistry & Physics, University of KwaZulu-Natal, Westville Campus, Chiltern Hills, Durban 4000,
South Africa
*
E-mail: jonnalagaddas@ukzn.ac.za
Received January 30, 2013
DOI 10.1002/jhet.2078
Published online 00 Month 2014 in Wiley Online Library (wileyonlinelibrary.com).
N N
N
N
N N
N
N
S
SH
SH
N
N
N
N
R
A new series of 4-(4-substitutedbenzylideneamino)-5-((1-methyl-1H-tetrazol-5-ylthio)methyl)-4H-1,2,4-
triazole-3-thiol derivatives (5a–k) are prepared using 4-amino-5-((1-methyl-1H-tetrazol-5-ylthio)methyl-
4H-1,2,4-triazole-3-thiol (4), as an intermediate compound. The structures of all the newly synthesized
products are established supported by their spectral 1H NMR, 13C NMR, FTIR, electrospray ionization mass
spectrometry (mass), and analytical data. All the compounds are screened for their insecticidal activity
against Plodia interpunctella, and six compounds exhibited significant activity.
J. Heterocyclic Chem., 00, 00 (2014).
INTRODUCTION
Similarly, several types of triazoles have been proved to
possess valuable pharmacological properties, such as antiviral
[16,17], antioxidant [18], antimalarial [19], anticonvulsant
[20,21], Alzheimer's disease [22], antidepressant [23,24], anti-
microbial [25,26], antitubercular [27,28], anti-inflammatory
[29,30], antiplatelet [31], antibacterial [32], antifungal
[33,34], anticancer [35,36], antiproliferative [37], and anti-
HIV [38,39] activities. In the pursuit of design of new drugs,
the development of hybrid molecules through the combination
of different pharmacophores in one frame could lead to com-
pounds with interesting biological properties. An integration
of these two moieties has potential to show synergistic effect
and could prove to be better insecticide. Hence, in the present
study, an attempt is made to synthesize molecules containing
both the tetrazole and triazole systems, and a series of new
derivatives (5a–k) of hybrid molecules were synthesized,
and their insecticidal activity was investigated.
Insects often impact the comfort and health of humans
and animals by biting and stinging activities and directly
cause irritation, hypersensitivity, and loss of blood, toxic-
ities, myiasis, and sometimes even death [1]. Indirect effect
of insects is that they reduce several million tons of crop
production every year. Unlike other insects, Plodia
interpunctella is a cosmopolitan pest that infects wide
range of stored products including nuts, beans, processed
food, and dried foods [2].
To overcome the problems associated with P.
interpunctella, several insect controls such as fumigants,
which contain methyl or phosphine, were developed.
Because of their stability in lower troposphere and impact
on ozone depletion, those were banned since 2004 [3].
Now, the insecticidal control research is focused on develop-
ment of new compounds that are highly potent, economical,
and safe to use [4,5]. The current scenario highlights the need
for the discovery of new lead compounds with simple
structure, which exhibit optimal insecticidal activity against
P. interpunctella and new mode of action. Tetrazole moiety
derivatives represent an interesting class of compounds
possessing a wide spectrum of biological activities. The
antibacterial [6], antifungal [7], anticonvulsant [8,9], analge-
sic [10], anticancer [11], anti-amoebic [12], antagonist [13],
antiviral [14], and antiproliferative [15] activities of various
tetrazole derivatives have been reported in literature.
RESULTS AND DISCUSSION
Chemistry. Compound 1 was treated with chloro acetic
acid 2 with acetone as solvent and in the presence of K2CO3
to give 2-(1-methyl-1H-tetrazol-5-ylthio)acetic acid (3). The
synthesis of cyclic amino-triazole (4) was performed by the
treatment of compound 3 with thiocarbohydrazide in
solvent-free condition. Finally, compound 4 was reacted
with different substituted aldehydes in the presence of few
2014 HeteroCorporation

S. Maddila, R. Pagadala, and S. B. Jonnalagadda
Vol 000
drops of concentrated sulfuric acid as a catalyst which upon
condensation gave a Schiff base in good yields (5a–k)
(Scheme 1). The structures of the newly synthesized
compounds were established and confirmed from their
systems containing substituted phenyl rings, which gave
excellent yields. The compounds, 5e, 5j, 5g, 5h, 5d, and
5f, showed significant insecticidal activity, whereas com-
pounds 5k, 5i, and 5c showed good activity. Thus, this
novel class of new tetrazole-linked triazole-containing
substituted phenyl derivatives emerges as a valuable lead
series with great potential as insecticidal agents. A system-
atic study on the structure–activity relationships and the
efficacy of evaluation might further improve the insecti-
cidal activity of these title compounds.
1
spectral H NMR, 13C NMR, FTIR, electrospray ionization
mass spectrometry (ESIMS), and analytical data. The
1
physical data, H NMR, 13C NMR, ESIMS and analytical
data for all the synthesized compounds are reported in
experimental protocols.
1
The H NMR spectra of compound (3) showed peak at
δ 11.94 ppm as a singlet for –COOH proton and a singlet at
δ 3.90 ppm for –NCH3 group protons. Similarly, compound
4 showed four singlets at δ 3.60, δ 3.96, δ 5.15 and
δ 13.57 ppm because of –SCH2, –NCH3, –NH2, and SH
group protons, respectively.
EXPERIMENTAL
Melting points were determined in open capillaries on a Mel-
Temp apparatus and are uncorrected. All the reactions were moni-
tored by TLC. The silica gel F254 plates were used for TLC in which
the spots were examined under UV light and then developed by an
iodine vapor. Column chromatography was performed with silica
gel (BDH 100–200 mesh). Solvents were purified according to stan-
dard procedures. The spectra were recorded with the following in-
struments: NMR, Varian Gemini 400 MHz (1H), 75MHz (13C)
spectrometer (Thermo Fisher, San Jose, CA); ESIMS, VG-
Autospec micromass, analyses of all the compounds were recorded
in LCQ Fleet, Thermo Fisher Instruments Limited. Organic extracts
were dried over anhydrous Na2SO4.
Biological assay results.
The insecticidal activities
against P. interpunctella of the library were investigated
using toosendanin, a commercial product as a standard
(100% activity). Table 1 summarizes the insecticidal
activity (%) of each compound as function of the exposure
duration. An examination of the results ( Table 1) reveals
that compounds 5e, 5j, 5g, 5h, 5d, and 5f exhibited
significant activity of 94 1.5, 92 1.2, 91 1.9, 91 1.5,
90 2.2, and 90 1.8, respectively, at 15μL/L comparable
with the standard. Furthermore, 5k, 5i, and 5c showed
good insecticidal activity of 84 1.7, 83 1.5, and 76 1.5,
respectively, under similar conditions. The least insecticidal
activity was associated with compounds 5a and 5b with
moderate values of 73 1.6 and 76 1.2, respectively. The
demonstration of synergic insecticidal activity by the new
compounds validates the proposed hypothesis.
Biological assay
Insecticidal assay. A total of 30 insects of P. interpunctella
(24 h age) were taken and placed into a 1000-mL glass jar. The
dose for different compounds was calculated on the basis of
nominal concentration and assumed 100% in the exposure glass
jar [40]. Filter paper was placed inside the jar, and the compounds
were transferred onto it. Then, varied concentrations ranging from
3, 6, 9, 12, to 15μL/L were prepared from the stock. For the
control, 15μL/L toosendanin was prepared, and it was considered
as standard. All experiments performed were executed in triplicate
runs at constant temperature (27 1°C), photo period (14L:10D)
and relative humidity (65% 5). The values were measured
averages SE. All chemicals and reagents used were of analytical
grade and obtained from Sigma.
CONCLUSION
In conclusion, we have described an efficient and benign
procedure for the synthesis of tetrazole-linked with triazole
Scheme 1. Synthesis pathway of tetrazole-linked triazole derivatives.
N
N
N
N
K CO
2
3
N
Cl
COOH
+
N
SH
reflux, 3h
N
S
COOH
N
1
2
3
NH NHCSNHNH
2
2
heat, 4h
CHO
N
N
N
N
N
N
N
N
R
N
N
S
N
DMF, Con H SO
2
S
4
N
N
SH
N
SH
5a-k
4
N
NH
2
R
Compd 5a
5b
5c
5d
5e
5f
5g
5h
5i
5j
5k
R
H
4-Me 4-OH 3,4-OH 3,4,5-F 2,4-Cl
2-NO2, 3-NO2, 4-F
4-CF3 4-Cl
3-F,
4-Cl
4-NO2
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2014
Tetrazole-Linked Triazole Derivatives
Table 1
Insecticidal activity of compounds (5a–k).
Insecticidal assay SE
Compounds
Concentration in μL/L
3 h
6 h
9 h
12 h
15 h
5a
5b
5c
5d
5e
5f
5g
5h
55.0 1.2
60.0 1.7
69.0 1.3
81.0 2.7
86.0 1.7
80.0 1.2
83.0 1.2
82.0 1.0
72.0 1.5
85.0 1.1
72.0 1.2
100.0 00
67.0 1.7
70.0 1.3
72.0 1.2
83.0 2.2
88.0 1.4
82.0 1.5
85.0 1.5
84.0 1.6
75.0 1.4
86.0 1.8
77.0 1.1
100.0 00
69.0 1.3
70.0 1.9
75.0 1.1
84.0 2.2
89.0 1.8
83.0 1.1
87.0 2.0
85.0 1.6
78.0 1.6
88.0 1.1
79.0 1.0
100.0 00
70.0 1.0
75.0 1.4
77.0 1.6
86.0 2.2
92.0 1.9
85.0 1.4
88.0 1.3
87.0 1.1
79.0 1.4
90.0 1.0
80.0 1.6
100.0 00
73.0 1.6
76.0 1.2
76.0 1.5
90.0 2.2
94.0 1.5
90.0 1.8
91.0 1.9
91.0 1.9
83.0 1.5
92.0 1.2
84.0 1.7
100.0 00
5i
5j
5k
Toosendanin
n = 3; SE, standard error.
Statistical analysis.
The data obtained from the test was
4-(4-Substitutedbenzylideneamino)-5-((1-methyl-1H-tetrazol-
5-ylthio)methyl)-4H-1,2,4-triazole-3-thiol derivatives (5a–k). An
equimolar mixture of compound 5 (10 mmol) and substituted
aldehydes (10 mmol), plus 3–4 drops of concentrated sulfuric acid
in N,N-dimethyl formamide (10mL) medium were stirred at room
temperature for 5–8 h. The reaction mixture was then poured into
ice-cold water to give a solid product, which was collected by
suction filtration and dried. The crude product was then
applied to Abbot's formula for mortality determination [41].
Mortality values in average for 24h exposure were submitted to
analysis for variance (one-way ANOVA) using the statistical
program (SPSS ver. 2012) for probit assay [42]. The outcomes
with p < 0.05 were considered as statistically significant.
2-(1-Methyl-1H-tetrazol-5-ylthio)acetic acid (3).
mixture of 5-mercapto-1-methyl-1H-tetrazole, 1 (10 mmol) in
acetone (20mL), K2CO3 (25 mmol) was added at room
To the
recrystallized from ethyl acetate to obtain pure compounds (5a–k).
4-(Benzylideneamino)-5-((1-methyl-1H-tetrazol-5-ylthio)methyl)-
4H-1,2,4-triazole-3-thiol (5a). Yield 92%; mp 236–238°C; IR
(cmꢀ1): 1583 (C¼C), 1496 (N¼N), 1275 (–N–N¼N–), 1189
temperature. This was followed by the addition of chloroacetic
acid, 2 (12 mmol). The reaction mixture was heated under reflux
for 3 h, and the completion of reaction was regularly monitored by
TLC. The reaction mixture was cooled to room temperature and
poured into ice water followed by extraction with ethyl acetate.
The combined organic layer was evaporated, recrystallized to
obtain 2-(1-methyl-1H-tetrazol-5-ylthio) acetic acid as solid.
1
(tetrazole); H NMR (DMSO-d6, 400 MHz): δ 13.60 (s, 1H, SH),
10.02 (s, 1H, CH), 7.70–7.45 (m, 5H, Ar-H), 3.85 (s, 3H, NCH3),
3.58 (s, 2H, SCH2); 13C NMR (DMSO-d6, 75MHz): δ 168.4,
160.2, 156.8, 148.4, 134.6, 131.2, 129.4, 128.9, 34.2, 30.1;
ESIMS: m/z 355 (M + Na)+. Anal. Calcd for C12H12N8S2: C,
43.36; H, 3.63; N, 33.71%; Found: C, 43.39; H, 3.61; N, 33.73%.
4-(4-Methylbenzylideneamino)-5-((1-methyl-1H-tetrazol-5-
ylthio)methyl)-4H-1,2,4-triazole-3-thiol (5b). Yield 77%; mp
253–255°C; IR (cmꢀ1): 1578 (C¼C), 1504 (N¼N), 1282 (–N–
N¼N–), 1197 (tetrazole); 1H NMR (DMSO-d6, 400 MHz): δ
13.56 (s, 1H, SH), 9.86 (s, 1H, CH), 7.59 (d, J = 8.0 Hz, 2H,
1
Yield 86%; mp 167–169°C; H NMR (CDCl3, 400 MHz): δ
11.94 (brs, 1H, COOH), 3.90 (s, 3H, NCH3), 3.58 (s, 2H,
SCH2); 13C NMR (CDCl3, 75 MHz): δ 168.5, 120.5, 38.9, 30.2;
ESIMS: m/z 197 (M + Na)+. Anal. Calcd for C4H6N4O2S: C,
27.58; H, 3.47; N, 32.17%; Found: C, 27.61; H, 3.44; N, 32.19%.
4-Amino-5-((1-methyl-1H-tetrazol-5-ylthio)methyl-4H-1,2,4-
triazole-3-thiol (4).
To a stirred solution of compound 3
(10 mmol), the thiocarbohydrazide (10 mmol) liquid was added and
heated in solvent-free condition for 4 h. The completion of reaction
was monitored by TLC. The reaction mixture was cooled to room
temperature, and the excess of acid compound was removed with
sodium bicarbonate solution. The solid was filtered, dried, and
recrystallized with DMF to give 4-amino-5-((1-methyl-1H-
tetrazol-5-ylthio)methyl-4H-1,2,4-triazole-3-thiol (4).
Ar-H), 7.27 (d, J = 8.0 Hz, 2H, Ar-H), 3.86 (s, 3H, NCH3), 3.55
(s, 2H, SCH2), 2.38 (s, 3H, CH3); 13C NMR (DMSO-d6,
75 MHz): δ 168.2, 159.28, 156.6, 148.2, 140.8, 130.9, 129.2,
33.4, 30.1, 24.3; ESIMS: m/z 369 (M + Na)+. Anal. Calcd for
C13H14N8S2: C, 45.07; H, 4.07; N, 32.34%; Found: C, 45.05; H,
4.09; N, 32.36%.
Yield 82%; mp 189–191°C; IR (cmꢀ1): 3458 (COOH), 1489
4-(4-Hydroxybenzylideneamino)-5-((1-methyl-1H-tetrazol-5-
1
ylthio)methyl)-4H-1,2,4-triazole-3-thiol (5c).
Yield 83%; mp
(N¼N), 1258 (–N–N¼N–), 1168 (tetrazole); H NMR (CDCl3,
221–223°C; IR (cmꢀ1): 3293 (OH), 1575 (C¼C), 1498 (N¼N),
1265 (–N–N¼N–), 1178 (tetrazole); 1H NMR (CDCl3,
400 MHz): δ 13.68 (s, 1H, SH), 10.86 (s, 1H, CH), 7.52 (s, 2H,
Ar-H), 6.96 (s, 2H, Ar-H), 3.98 (s, 3H, NCH3), 3.90 (brs, 1H,
OH), 3.59 (s, 2H, SCH2); 13C NMR (CDCl3, 75 MHz): δ 168.4,
400 MHz): δ 13.57 (s, 1H, SH), 5.15 (s, 2H, NH2), 3.96 (s, 3H,
NCH3), 3.60 (s, 2H, SCH2); 13C NMR (CDCl3, 75 MHz): δ
172.1, 168.2, 160.5, 34.7, 30.4; ESIMS: m/z 245 (M + H)+. Anal.
Calcd for C5H8N8S2: C, 24.58; H, 3.30; N, 45.87%: Found: C,
24.54; H, 3.27; N, 45.91%.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

S. Maddila, R. Pagadala, and S. B. Jonnalagadda
Vol 000
160.8, 160.2, 156.9, 148.3, 130.8, 126.4, 116.2, 33.8, 30.2;
ESIMS: m/z 349 (M + H)+. Anal. Calcd for C12H12N8OS2: C,
41.37; H, 3.47; N, 32.16%; Found: C, 41.39; H, 3.49; N, 32.13%.
4-(3,4-Difluorobenzylideneamino)-5-((1-methyl-1H-tetrazol-
4-(4-Chloro-3-fluorobenzylideneamino)-5-((1-methyl-1H-
tetrazol-5-ylthio)methyl)-4H-1,2,4-triazole-3-thiol (5j). Yield
80%; mp 218–220°C; IR (cmꢀ1): 1592 (C¼C), 1508 (N¼N),
1280 (–N–N¼N–), 1173 (tetrazole); 1H NMR (CDCl3, 400MHz):
δ 13.72 (s, 1H, SH), 10.83 (s, 1H, CH), 7.58–7.27 (m, 3H, Ar-H),
3.97 (s, 3H, NCH3), 3.64 (s, 2H, SCH2); 13C NMR (CDCl3,
75MHz): δ 168.3, 162.9, 160.0, 156.9, 148.1, 133.5, 130.8,
126.2, 123.0, 115.5, 34.2, 33.0; ESIMS: m/z 385 (M + H)+. Anal.
Calcd for C12H10ClFN8S2: C, 37.46; H, 2.64; N, 29.20%; Found:
C, 37.48; H, 2.61; N, 29.22%.
5-ylthio)methyl)-4H-1,2,4-triazole-3-thiol (5d).
Yield 86%;
mp 261–263°C; IR (cmꢀ1): 1585 (C¼C), 1503 (N¼N), 1276
(–N–N¼N–), 1189 (tetrazole); 1H NMR (CDCl3, 400 MHz): δ
13.72 (s, 1H, SH), 10.89 (s, 1H, CH), 7.60 (d, J = 8.2 Hz, 2H,
Ar-H), 7.34 (s, 1H, Ar-H), 3.98 (s, 3H, NCH3), 3.62 (s, 2H,
SCH2); 13C NMR (CDCl3, 75 MHz): δ 168.4, 160.3, 156.9,
151.8, 149.7, 148.2, 131.0, 126.5, 117.4, 115.6, 34.0, 30.1;
ESIMS: m/z 391 (M + Na)+. Anal. Calcd for C12H10F2N8S2: C,
39.12; H, 2.74; N, 30.42%; Found: C, 39.09; H, 2.75; N, 30.44%.
4-(3,4,5-Trifluorobenzylideneamino)-5-((1-methyl-1H-tetrazol-
5-ylthio)methyl)-4H-1,2,4-triazole-3-thiol (5e). Yield 93%; mp
243–245°C; IR (cmꢀ1): 1566 (C¼C), 1503 (N¼N), 1287
(–N–N¼N–), 1195 (tetrazole); 1H NMR (DMSO-d6, 400 MHz): δ
13.75 (s, 1H, SH), 10.92 (s, 1H, CH), 7.64 (s, 1H, Ar-H), 7.52 (s, 1H,
Ar-H), 3.99 (s, 3H, NCH3), 3.64 (s, 2H, SCH2); 13C NMR (DMSO-
d6, 75MHz): δ 168.3, 160.5, 157.1 151.3, 148.2, 142.5, 132.6, 111.4,
34.1, 30.0; ESIMS: m/z 409 (M + Na)+. Anal. Calcd for C12H9F3N8S2:
C, 37.30; H, 2.35; N, 29.0%; Found: C, 37.28; H, 2.37; N, 29.03%.
4-(2,4-Dichlorobenzylideneamino)-5-((1-methyl-1H-tetrazol-
4-(4-Nitrobenzylideneamino)-5-((1-methyl-1H-tetrazol-5-ylthio)
methyl)-4H-1,2,4-triazole-3-thiol (5k). Yield 90%; mp 198–200°
C; IR (cmꢀ1): 1583 (C¼C), 1514 (N¼N), 1291 (–N–N¼N–), 1179
(tetrazole); 1H NMR (CDCl3, 400 MHz): δ 13.74 (s, 1H, SH),
10.82 (s, 1H, CH), 8.31 (d, J= 8.5 Hz, 2H, Ar-H), 7.96 (d,
J= 9.0 Hz, 2H, Ar-H), 4.0 (s, 3H, NCH3), 3.63 (s, 2H); 13C NMR
(CDCl3, 75MHz): δ 168.2, 160.1, 156.8, 150.2, 148.1, 140.0,
130.2, 124.0, 34.0, 30.1; ESIMS: m/z 400 (M + Na)+. Anal. Calcd
for C12H11N9O2S2: C, 38.20; H, 2.95; N, 33.42%; Found: C, 38.23;
H, 2.93; N, 33.44%.
Acknowledgments. The authors are thankful to the School of
Chemistry and Physics, University of KwaZulu-Natal for the
financial support and research facilities.
5-ylthio)methyl)-4H-1,2,4-triazole-3-thiol (5f).
Yield 89%;
mp 229–231°C; IR (cmꢀ1): 1573 (C¼C), 1508 (N¼N), 1280
(–N–N¼N–), 1176 (tetrazole); 1H NMR (CDCl3, 400 MHz): δ
13.74 (s, 1H, SH), 10.86 (s, 1H, CH), 7.74–7.51 (m, 3H, Ar-H),
3.97 (s, 3H, NCH3), 3.62 (s, 2H, SCH2); 13C NMR (CDCl3,
75 MHz): δ 168.2, 160.1, 156.9, 148.0, 138.1, 135.4, 131.6,
130.5, 127.0, 34.2, 30.0; ESIMS: m/z 402 (M + H)+. Anal.
Calcd for C12H10Cl2N8S2: C, 35.92; H, 2.51; N, 27.92%;
Found: C, 35.95; H, 2.53; N, 27.90%.
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4-(2-Nitro-4-(trifluoromethyl)benzylideneamino)-5-((1-methyl-
1H-tetrazol-5-ylthio)methyl)-4H-1,2,4-triazole-3-thiol (5g). Yield
90%; mp 216–218°C; IR (cmꢀ1): 1592 (C¼C), 1502 (N¼N),
1287 (–N–N¼N–), 1198 (tetrazole); 1H NMR (CDCl3, 400MHz):
δ 13.75 (s, 1H, SH), 10.88 (s, 1H, CH), 7.93–7.80 (m, 2H, Ar-H),
7.56 (s, 1H, Ar-H), 3.99 (s, 1H, NCH3), 3.64 (s, 2H, SCH2); 13
C
NMR (CDCl3, 75MHz): δ 168.3, 160.1, 156.9, 148.0, 134.3,
131.6, 131.3, 130.5, 123.2, 121.8, 34.2, 30.1; ESIMS: m/z 446
(M + H)+. Anal. Calcd for C13H10F3N9O2S2: C, 35.06; H, 2.26; N,
28.30%; Found: C, 35.04; H, 2.28; N, 28.32%.
4-(4-Chloro-3-nitrobenzylideneamino)-5-((1-methyl-1H-tetrazol-
5-ylthio)methyl)-4H-1,2,4-triazole-3-thiol (5h). Yield 82%; mp
277–279°C; IR (cmꢀ1): 1566 (C¼C), 1510 (N¼N), 1283
(–N–N¼N–), 1180 (tetrazole); 1H NMR (CDCl3, 400MHz): δ
13.72 (s, 1H, SH), 10.84 (s, 1H, CH), 7.78–7.56 (m, 3H, Ar-H),
3.97 (s, 3H, NCH3), 3.62 (s, 2H, SCH2); 13C NMR (CDCl3,
75MHz): δ 168.2, 160.0, 156.9, 148.2, 136.8, 132.7, 131.8,
130.0, 124.3, 34.1, 30.0; ESIMS: m/z 412 (M + H)+. Anal. Calcd
for C12H10ClN9O2S2: C, 35.01; H, 2.46; N, 30.62%; Found: C,
35.03; H, 2.44; N, 30.65%.
4-(4-Fluorobenzylideneamino)-5-((1-methyl-1H-tetrazol-5-
ylthio)methyl)-4H-1,2,4-triazole-3-thiol (5i).
Yield 81%; mp
209–211°C; IR (cmꢀ1): 1578 (C¼C), 1499 (N¼N), 1280
(–N–N¼N–), 1192 (tetrazole); 1H NMR (CDCl3, 400MHz): δ
13.74 (s, 1H, SH), 10.85 (s, 1H, CH), 7.74 (d, J = 8.3Hz, 2H,
Ar-H), 7.56 (d, J = 8.3 Hz, 2H, Ar-H), 3.99 (s, 3H, NCH3), 3.63
(s, 2H, SCH2); 13C NMR (CDCl3, 75 MHz): δ 168.4, 165.2,
160.1, 156.8, 148.0, 130.8, 129.5, 115.6, 34.2, 33.0; ESIMS: m/z
373 (M +Na)+. Anal. Calcd for C12H11FN8S2: C, 41.13; H, 3.17;
N, 32.02%; Found: C, 41.16; H, 3.15; N, 32.05%.
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