The synthesis of 1-(1-phenyl-1H-tetrazole-5-ylthiol)-acetyl-4-aroyl- thiosemicarbazides and 2-aroylamino-5-(1-phenyl-1H-tetrazole-5-ylthiolmethylene) - 1,3,4-thiadiazoles

Article abstract of DOI:10.1080/10426500500366434

A series of 1-(1-phenyl-1H-tetrazole-5-ylthiol)acetyl-4- aroylthiosemicarbazides were synthesized in good to excellent yields under phase transfer catalytic conditions. By the cyclization of compounds 3a-i in concentrated H₂SO₂ at 0°

Full text of DOI:10.1080/10426500500366434

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Phosphorus, Sulfur, and Silicon
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The Synthesis of 1-(1-
Phenyl-1H-tetrazole-5-
ylthiol)-acetyl-4-aroyl-
thiosemicarbazides and 2-
Aroylamino-5- (1-phenyl-1H-
tetrazole-5-ylthiolmethylene)-
1,3,4-thiadiazoles
Tai-Bao Wei a , Man-Lin Li a , Qi Lin a , Hong Liu a &
You-Ming Zhang a
a Department of Chemistry, Gansu Key Laboratory
of Polymer Materials, Northwest Normal University,
Lanzhou, Gansu, P. R. China
Published online: 01 Feb 2007.
To cite this article: Tai-Bao Wei , Man-Lin Li , Qi Lin , Hong Liu & You-Ming
Zhang (2006) The Synthesis of 1-(1-Phenyl-1H-tetrazole-5-ylthiol)-acetyl-4-aroyl-
thiosemicarbazides and 2-Aroylamino-5- (1-phenyl-1H-tetrazole-5-ylthiolmethylene)-
1,3,4-thiadiazoles, Phosphorus, Sulfur, and Silicon and the Related Elements, 181:7,
1583-1592, DOI: 10.1080/10426500500366434
To link to this article: http://dx.doi.org/10.1080/10426500500366434
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Phosphorus, Sulfur, and Silicon, 181:1583–1592, 2006
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500500366434
The Synthesis of 1-(1-Phenyl-1H-tetrazole-5-ylthiol)-
acetyl-4-aroyl-thiosemicarbazides and 2-Aroylamino-5-
(1-phenyl-1H-tetrazole-5-ylthiolmethylene)-
1,3,4-thiadiazoles
Tai-Bao Wei
Man-Lin Li
Qi Lin
Hong Liu
You-Ming Zhang
Department of Chemistry, Gansu Key Laboratory of Polymer Materials,
Northwest Normal University, Lanzhou, Gansu, P. R. China
A
series of 1-(1-phenyl-1H-tetrazole-5-ylthiol)acetyl-4-aroylthiosemicarbazides
were synthesized in good to excellent yields under phase transfer cat-
alytic conditions. By the cyclization of compounds 3a–i in concentrated
H SO at 0◦C,2-aroylamino-5-(1-phenyl-1H-tetrazole-5-ylthiolmethylene)-1,3,4-
2
4
thiadiazoles were obtained in high yields. The structures of the products were es-
1
13
tablished by elemental analysis, IR , H NMR, and C NMR.
Keywords 2,5-Disubstituted-1,3,4-thiadiazole; aroylthiosemicarbazide; phase transfer
catalysis; tetrazole
INTRODUCTION
Many compounds containing tetrazole rings have been found to have
a wide range of biological properties.1 1H-tetrazole-5-thiol deriva-
tives have been found to have antiviral, antibacterial, anthelmintic,
and anti-inflammatory properties.1,2 These functional groups play
important roles in coordination chemistry, material science applica-
tions, and especially medicinal chemistry.1,3 New uses for this unique
Received June 6, 2005; accepted August 11, 2005.
This work was supported by the National Natural Science Foundation (No. 20371040)
of China, the key project of Ministry of Education of China (No. 205161), the Natu-
ral Science Foundation (3YS051-A25-010, No. 031-A21-004, 3ZS041-A25-007) of Gansu
province, who are gratefully acknowledged.
Address correspondence to You-Ming Zhang, Department of Chemistry, Gansu Key
Laboratory of Polymer Materials, Northwest Normal University, Lanzhou, Gansu,
730070, P. R. China. E-mail: zhangnwnu@126.com
1583

1584
T.-B. Wei et al.
class of heterocyclic derivatives continue to emerge in pharmaceutical
applications3−5 and antibiotics intermediates.6
Recently, the importance of N C S linkage has been well stressed.
The linkage is an essential structural feature, which is responsible for
various biological activities in many well-known organic sulphur pesti-
cides, such as dithiocarbamates, thioureas, and thiosemicarbazides.7,8
The survey of the literature revealed that some thiosemicarbazides con-
taining a tetrazole ring had been used as plant growth regulators.9−11
Moreover, aroylthiosemicarbazide is also valuable as a synthetic inter-
mediate for the preparation of some thiadiazole derivatives.12
It is well established that various substituted 1,3,4-thiadiazoles have
become very useful compounds in medicine, agriculture, and many
fields of technology.13,14 Some of these compounds exhibit interesting
pharmacological properties, like antitubercular and anti-inflammatory
properties.15 A large number of 1,3,4-thiadiazoles have been patented
in the agricultural field as herbicides, fungicides, and bactericides.16,17
These observations prompted us to synthesize some new compounds
wherein biologically active moieties are present. In addition, in order
to improve the biological ability of compounds, much attention has
been paid to the development of the functional group in the ring. It
is significant that the combined effect of all the entities will result in
increased biological activity. In view of these and in continuation of
our earlier work on the synthesis of thiosemicarbazide and thiourea
derivatives,18−21 we report some new compounds containing tetrazole
rings and thiadiazole rings. All of these compounds have never been
reported before.
The reaction sequences leading to the formation of different title com-
pounds are outlined in Schemes 1 and 2. Our synthetic approach was
aimed at creating hydrazide 1 and a series of aroyl isothiocyanates 2.
They were key intermediates in producing title compounds. Hydrazide
1 was prepared according to the procedure available in the literature.2
Aroyl isothiocyanates are versatile reagents, and their chemistry has
received considerable recent interest.23 We could employ them as good
intermediates to prepare easily various thiosemicarbazides. In this
procedure, aroyl chloride was treated with ammonium thiocyanate
(NH4SCN) in ethyl acetate under the condition of solid–liquid phase
transfer catalysis using PEG-400 as the catalyst to give the correspond-
ing aroyl isothiocyanate in quantitative yields. On the contrary, we
could not get any products or good yields when no PEG-400 or other
PTC participated in the reaction. The target products 3a–i could be
obtained by the addition reaction between aroyl isothiocycanates with
hydrazide. Since terazole hydrazide is insoluble in ethyl acetate, we
added it portionwise into a solution of 2 in a flask with rigorous stirring

Thiosemicarbazides and Thiadiazoles
1585
SCHEME 1
for 1–2 h at a refluxing temperature. The precipitate was separated
out and recrystallized from DMF-EtOH-H2O to give 3a–i. Compound 3
was treated with concentrated sulphuric acid at 0◦C in an ice bath with
constant stirring for 1–2 h. Then, the reaction mixture was poured into
150 mL of ice water. The precipitate formed was filtered and washed
SCHEME 2 R: a: o-Cl, b: p-Cl, c: m-Cl, d: p-F, e: H, f: p-Br, g: p-CH3,h:
p-OCH2CH3,i: p-I.

1586
T.-B. Wei et al.
with water and recrystallized from DMF-EtOH-H2O to give 4a–i in good
to excellent yields.
In this procedure, we employed concentrated sulphuric acid instead
of using acetic acid as a dehydration reagent. As a rule, using acetic acid
as a dehydration reagent had the disadvantages of relatively longer
reaction times (5–6 h), and the reaction mixture had to reflux at a high
temperature. Furthermore, since acetic acid was not a good solvent,
for compound 3, in order to dissolve the reactant, we had to employ
some other solvent, such as DMF or DMSO, although it was not easily
removed due to its high boiling point. The use of concentrated H2SO4
could overcome these shortcomings. It is not only a good dehydration
reagent but also a useful solvent for many organic compounds. Here we
used it to successfully prepare the title compounds.
In conclusion, this is a facile and convenient method for the syn-
thesis of title compounds under solid–liquid phase transfer catalytic
conditions. This method possesses the advantages of mild conditions,
a simple operation, short reaction times, and high yields; also, the cat-
alyst PEG-400 is inexpensive, relatively nontoxic, highly stable, and
easily available. The biological properties of title compounds are under
investigation.
EXPERIMENTAL
All reagents were purchased and without further purification. Melt-
ing points were determined in open capillaries and are uncorrected.
IR spectra were recorded as KBr discs on an Alpha Centauri FT-IR
1
spectrophotometer. H NMR and 13C NMR spectra were recorded on
a Varian Mercury Plus-400 instrument (400 MHz) using DMSO-d6 as
a solvent and TMS as an internal reference. Elemental analysis was
determined on a PE-2400 CHN instrument.
The General Procedure
1-phenyl-1H-5-mercapto-tetrazole was prepared by methods in the
literature.22 (1-phenyl-1H-tetrazole-5-ylthiol) acetic acid hydrazide
(compound 1) was prepared by methods in the literature.2
The General Procedure for the Preparation of 3a–i
A mixture of 0.91 g dried and powdered NH4SCN (12 mmol), Aroyl
chloride (11 mmol), and PEG-400 (0.1 mL) in ethyl acetate (15 mL)
was stirred in a flask at r.t. for 1–2 h. The mixture was filtered to
isolate inorganic salt NH4Cl and washed with 3 × 10 mL EtOAc to

Thiosemicarbazides and Thiadiazoles
1587
acquire a solution of 2. Then, (1-phenyl-1H-tetrazole-5-ylthiol) acetic
acid hydrazide 1 (10 mmol) was slowly added into it with constant
stirring at a refluxing temperature for 1–2 h. The precipitate formed
was filtered and recrystallized from DMF-EtOH-H2O to give pure
products 3a–i.
The General Procedure for the Preparation of 4a–i
A portion of 3 (5 mmoL) was dissolved in concentrated sulphuric acid
(2.5 mL) in ice bath; the solution was kept at 0◦C for 2 h with constant
stirring and then poured into 150 mL of water with an excess of crushed
ice. It was stirred well and allowed to stand for 1–2 h. The residue was
filtered and washed with ice water and then recrystallized from DMF-
EtOH-H2O to give pure products 4a–i.
1-(1-Phenyl-1H-tetrazole-5-ylthiol)acetyl-4-
(2-chlorobenzoyl)thiosemicarbazide (3a)
Yield 76%, m.p. 158–160◦C. IR(KBr) υ (cm−1): 3203, 1687, 1593,
1313, 1183. Anal. calc. for C17H14O2S2ClN7: C, 45.59; H, 3.15; N, 21.90.
1
Found: C, 45.76; H, 3.01; N, 21.69. H NMR(DMSO-d6): δ = 12.46 (s,
1H, N NH CS), 12.19(s, 1H, CS NH CO), 11.44 (s, 1H, CO NH N),
7.43–7.73 (m, 9H, Ar-H), 4.41(s, 2H, SCH2 ). 13C NMR (DMSO-d6):
δ = 176.26 (C S), 167.39 (O C-Ar), 163.64 ( CONH), 153.68 (N C N),
134.03, 133.04, 132.20, 130.75, 130.11, 129.97, 129.6, 129.30, 127.15,
124.56(Ar-C), 34.72 ( SCH2 ).
1-(1-Phenyl-1H-tetrazole-5-ylthiol)acetyl-4-(4-chlorobenzoyl)-
thiosemicarbazide (3b)
Yield 92%, m.p. 213–214◦C. IR(KBr) υ (cm−1): 3172, 1666, 1595,
1311, 1171. Anal. calc. for C17H14O2S2ClN7: C, 45.59; H, 3.15; N, 21.90.
1
Found: C, 45.64; H, 2.90; N, 21.71. H NMR(DMSO-d6): δ = 12.62 (s,
1H, N NH CS), 11.87(s, 1H, CS NH CO), 11.40(s, 1H, CO NH N),
7.56–8.00(m, 9H, Ar-H), 4.38 (s, 2H, SCH2 ). 13C NMR (DMSO-d6):
δ = 176.80(C S), 167.05(O C-Ar), 163.63( CONH), 153.68(N C N),
138.13, 133.05, 132.15, 130.76, 130.65, 130.11, 128.56, 124.55(Ar-C),
34.78( SCH2 ).
1-(1-Phenyl-1H-tetrazole-5-ylthiol)acetyl-4-
(3-chlorobenzoyl)thiosemicarbazide (3c)
Yield 79%, m.p. 188–190◦C. IR(KBr) υ (cm−1): 3130, 1675, 1572,
1302, 1170. Anal. calc. for C17H14O2S2ClN7: C, 45.59; H, 3.15; N, 21.90.
1
Found: C, 45.72; H, 3.15; N, 21.95. H NMR (DMSO-d6): δ = 12.62(s,
1H, N NH CS), 11.91(s, 1H, CS NH CO), 11.42 (s,1H, CO NH N),

1588
T.-B. Wei et al.
7.50–7.99(m, 9H, Ar-H), 4.39(s, 2H, SCH2 ). 13C NMR (DMSO-d6):
δ = 176.64(C S), 166.68(O C-Ar), 163.63 ( CONH), 153.68 (N C N),
133.84, 133.18, 133.05, 132.85, 130.71, 130.36, 130.10, 128.55, 127.5,
124.5(Ar-C), 34.81( SCH2 ).
1-(1-Phenyl-1H-tetrazole-5-ylthiol)acetyl-4-(4-
fluorobenzoyl)thiosemicarbazide (3d)
Yield 89%, m.p. 214–215◦C IR(KBr) υ (cm−1): 3169, 1668, 1601,
1311, 1170. Anal. calc. for C17H14O2S2FN7: C, 47.12; H, 3.34; N,
22.79. Found: C, 47.33; H, 3.25; N, 22.74. 1H NMR (DMSO-d6): δ =
12.62 (s, 1H, N NH CS), 11.82(s, 1H, CS NH CO), 11.40 (s, 1H,
CO NH N), 7.31–8.04 (m, 9H, Ar-H), 4.38(s, 2H, SCH2 ). 13C
NMR(DMSO-d6):δ = 176.84(C S), 166.6(O C-Ar), 163.67 ( CONH),
153.68 (N C N), 133.05, 131.87, 131.77, 130.73, 130.1, 128.31, 124.55,
115.64, 115.42 (Ar-C), 34.77( SCH2 ).
1-(1-Phenyl-1H-tetrazole-5-ylthiol)acetyl-4-
benzoylthiosemicarbazide (3e)
Yield 90%, m.p. 197–199◦C IR(KBr) υ (cm−1): 3125, 1672, 1573,
1300, 1166. Anal. calc. for C17H15O2S2FN7: C 49.39; H 3.63; N 23.73.
1
Found: C 49.35; H 3.58; N 23.62. H NMR(DMSO-d6): δ = 4.38(s, 2H,
CH2 ), 7.49–7.95(m, 10H, Ar-H), 12.70(s, 1H, N NH CS), 11.78(s,
1H, CS NH CO), 11.39(s, 1H, CO NH N). 13C NMR(DMSO-d6):
δ = 176.93 (C S), 168.1(O C Ar), 163.58 ( CONH), 153.69(N C N),
133.2, 133.04, 131.80, 130.75, 130.11, 128.77, 128.47, 124.57(Ar-C),
34.76( SCH2 ).
1-(1-Phenyl-1H-tetrazole-5-ylthiol)acetyl-4-(4-bromobenzoyl)-
thiosemicarbazide (3f)
Yield 88%, m.p. 206–208◦C. IR(KBr) υ (cm−1): 3169, 1670, 1589,
1313, 1170. Anal. calc. for C17H14O2S2BrN7: C, 41.47; H, 2.85; N, 19.92.
Found: C, 41.30; H, 2.40; N, 19.94.1H NMR (DMSO-d6): δ = 12.62(s,
1H, N NH CS), 11.87(s, 1H, CS NH CO), 11.39 (s, 1H, CO NH N),
7.62–7.91(m, 9H, Ar-H), 4.37(s, 2H, SCH2 ). 13C NMR (DMSO-d6):
δ = 176.79 (C S),167.2(O C-Ar), 163.63( CONH), 153.68 (N C N),
133.05, 131.51, 131.03, 130.9, 130.75, 130.1, 127.2, 124.56(Ar-C),
34.78( SCH2 ).
1-(1-Phenyl-1H-tetrazole-5-ylthiol)acetyl-4-
(4-methylbenzoyl)thiosemicarbazide (3g)
Yield 91%, m.p. 196–198◦C. IR(KBr) υ (cm−1): 3180, 1668, 1613,
1300, 1172. Anal. calc. for C18H17O2S2N7: C, 50.59; H, 3.98; N, 22.95.

Thiosemicarbazides and Thiadiazoles
1589
Found: C, 50.70; H, 3.94; N, 22.95. 1H NMR(DMSO-d6): δ = 2.36(s, 3H,
CH3), 4.42(s, 2H, SCH2 ), 12.78(s, 1H, N NH CS), 11.72 (s, 1H,
CS NH CO), 11.43(s, 1H, CO NH N), 7.33–7.91 (m, 9H, Ar-H); 13C
NMR (DMSO-d6): δ = 177.0(C S), 167.9(O C-Ar), 163.58 ( CONH),
153.7 (N C N), 143.7, 133.1, 130.73, 130.1, 129.06, 128.88, 128.84,
124.54(Ar-C), 34.80( SCH2 ), 21.19(Ar-CH3).
1-(1-Phenyl-1H-tetrazole-5-ylthiol)acetyl-4-
(4-ethyloxylbenzoyl) thiosemicarbazide (3h)
Yield 95%, m.p. 190–192◦C. IR(KBr) υ (cm−1): 3163, 1671, 1603,
1310, 1180. Anal. calc. for C19H19O3S2N7: C, 49.60; H, 4.25; N,
21.21. Found: C, 49.90; H, 4.16; N, 21.44. 1H NMR (DMSO-
d6): δ = 12.77(N NH CS), 11.58(s, 1H, CS NH CO), 11.36 (s, 1H,
CO NH N), 7.00–7.97(m, 9H, Ar-H), 4.35(s,2H, SCH2 ), 4.10(q, 2H,
OCH2 ), 1.33 (t, 3H, CH3). 13C NMR(DMSO-d6): δ = 177.11 (C S),
167.30(O C-Ar), 163.51( CONH), 153.68(N C N), 162.45, 133.04,
131.1, 130.75, 130.1, 124.57, 123.31, 114.17(Ar-C), 34.75( SCH2 ),
30.79( OCH2 ), 63.64( CH3).
1-(1-Phenyl-1H-tetrazole-5-ylthiol)acetyl-4-(4-iodobenzoyl)
thiosemicarbazide (3i)
Yield 70%, m.p. 198–200◦C. IR(KBr) υ (cm−1): 3195, 1671, 1577, 1305,
1162. Anal. calc. for C17H14O2S2N7I: C, 37.85; H, 2.60; N, 18.19. Found:
C, 38.06; H, 2.73; N, 18.08. 1H NMR (DMSO-d6):δ = 12.63 (N NH CS),
11.84(s, 1H, CS NH CO), 11.38 (s, 1H, CO NH N), 7.63–7.94 (m, 9H,
Ar-H), 4.37(s, 2H, SCH2 ). 13C NMR(DMSO-d6): δ = 176.78 (C S),
167.48(O C-Ar), 162.97 ( CONH), 153.67(N C N), 137.48, 133.02,
131.27, 131.19, 130.69, 130.55, 130.10, 124.55(Ar-C), 34.77( SCH2 ).
2-(2-Chlorobenzoylamino)-5-(1-phenyl-1H-tetrazole-5-
ylthiolmethylene)-1,3,4-thiadiazole (4a)
Yield 78%, m.p. 163–164◦C. IR(KBr) υ (cm−1): 3145, 1679, 1592, 1389,
1309, 689. Anal. calc. for C17H12OS2N7Cl: C, 47.50; H, 2.79; N, 22.82.
Found: C, 47.75; H, 2.78; N, 23.10. 1H NMR(DMSO-d6): δ = 13.25(s, 1H,
NH ), 7.48–7.71(m, 9H, Ar-H), 5.04(s, 2H, SCH2
)
13C NMR(DMSO-
d6):δ = 165.02, 160.52, 159.64, 153.33, 133.74, 132.90, 132.31, 130.78,
130.37, 130.06, 129.89, 129.63, 127.32, 124.61, 30.96.
2-(4-Chlorobenzoylamino)-5-(1-phenyl-1H-tetrazole-
5-ylthiolmethylene)-1,3,4-thiadiazole (4b)
Yield 86%, m.p. 208–210◦C. IR(KBr) υ (cm−1): 3179, 1674, 1594, 1390,
1314, 682. Anal. calc. for C17H12OS2N7Cl: C, 47.50; H, 2.79; N, 22.82.

1590
T.-B. Wei et al.
1
Found: C, 47.74; H, 2.51; N, 22.82. H NMR (DMSO-d6): δ = 13.13 (s,
1H, NH ), 7.53–8.10 (m, 9H, Ar-H), 4.99 (s, 2H, SCH2 ).
2-(3-Chlorobenzoylamino)-5-(1-phenyl-1H-tetrazole-5-
ylthiolmethylene)-1,3,4-thiadiazole (4c)
Yield 87%, m.p. 228–230◦C. IR(KBr) υ (cm−1): 3165, 1670, 1595, 1402,
1313, 692. Anal. calc. for C17H12OS2N7Cl: C, 47.50; H, 2.79; N, 22.82.
Found: C, 47.56; H, 2.69; N, 22.92. 1H NMR(DMSO-d6):δ = 13.11 (s, 1H,
NH ), 7.55–8.14 (m, 9H, Ar-H), 4.98(s,2H, SCH2 ).
2-(4-Fluorobenzoylamino)-5-(1-phenyl-1H-tetrazole-5-
ylthiolmethylene)-1,3,4-thiadiazole (4d)
Yield 90%, m.p. 232–234◦C. IR(KBr) υ (cm−1): 3177, 1675, 1601,
1413, 1315, 684. Anal. calc. for C17H12OS2N7F: C, 49.39; H, 2.91; N,
23.73. Found: C, 49.62; H, 2.53; N, 23.66. 1H NMR (DMSO-d6): δ = 13.08
(s, 1H, NH ), 7.36–8.18 (m, 9H, Ar-H), 4.98(s, 2H, SCH2 ). 13C
NMR(DMSO-d6): δ = 164.17, 163.65, 160.16, 153.33, 132.90, 131.43,
131.33, 130.78, 130.07, 128.00, 124.63, 115.80, 30.96.
2-Benzoylamino-5-(1-phenyl-1H-tetrazole-5-ylthiolmethylene)-
1,3,4-thiadiazole (4e)
Yield 93%, m.p. 214–216◦C IR(KBr) υ (cm−1): 3167, 1660, 1597, 1410,
1304, 702. Anal. calc. for C17H13OS2N7: C, 51.64; H, 3.29; N, 24.81.
Found: C, 51.60; H, 2.98; N, 24.67. 1H NMR (DMSO-d6): δ = 4.99(s,
2H, CH2 ), 13.07(s, 1H, NH ), 7.52–8.10(m, 10H, Ar-H). 13C NMR
(DMSO-d6): δ = 165.22, 160.60, 160.13, 153.32, 133.07, 132.90, 131.40,
130.77, 130.05, 128.70, 128.42, 124.62, 30.96.
2-(4-Bromobenzoylamino)-5-(1-phenyl-1H-tetrazole-5-
ylthiolmethylene)-1,3,4-thiadiazole (4f)
Yield 79%, m.p. 230–232◦C IR(KBr) υ (cm−1): 3181, 1674, 1589,
1389, 1311, 690. Anal. calc. for C17H13OS2N7Br: C, 43.04; H, 2.53; N,
20.68. Found: C, 43.08; H, 2.43; N, 20.62. 1H NMR (DMSO-d6): δ =
13.14(s, 1H, NH ), 7.57–8.02 (m, 9H, Ar-H), 4.99(s, 2H, SCH2 ). 13
C
NMR(DMSO-d6): δ = 164.46, 160.68, 160.12, 153.29, 132.90, 131.70,
130.71, 130.60, 130.45, 130.04, 127.10, 124.50, 30.99.
2-(4-Methylbenzoylamino)-5-(1-phenyl-1H-tetrazole-5-
ylthiolmethylene)-1,3,4-thiadiazole (4g)
Yield 82%, m.p. 205–206◦C IR(KBr) υ (cm−1): 3165, 1651, 1607, 1398,
1302, 683. Anal. calc. for C18H15OS2N7: C, 49.60; H, 4.25; N, 21.21.
1
Found: C, 49.90; H, 4.16; N, 21.44. H NMR (DMSO-d6): δ = 13.08 (s,

Thiosemicarbazides and Thiadiazoles
1591
1H, NH ), 7.45–8.13 (m, 9H, Ar-H), 5.10(s, 2H, SCH2 ), 2.60(s,
3H, CH3). 13C NMR(DMSO-d6): δ = 164.93, 160.60, 160.05, 153.31,
143.46, 132.89, 131.90, 130.75, 130.04, 129.24, 128.45, 124.61, 30.94,
21.13.
2-(4-Ethyloxylbenzoylamino)-5-(1-phenyl-1H-tetrazole-5-
ylthiolmethylene)-1,3,4-thiadiazole (4h)
Yield 86%, m.p. 197–199◦C IR(KBr) υ (cm−1): 3167, 1659, 1605, 1391,
1299, 684. Anal. calc. for C19H17O2S2N7: C, 51.92; H, 3.90; N, 22.31.
Found: C, 51.64; H, 3.72; N, 22.29. 1H NMR(DMSO-d6):δ = 12.85(s, 1H,
NH ), 4.97(s, 2H, SCH2 ), 4.09(q,2H, OCH2 ), 1.33(t, 3H, CH3),
7.02–8.09 (m, 9H, Ar-H). 13C NMR(DMSO-d6): δ = 164.23, 160.23,
159.90, 153.33, 132.90, 130.75, 130.56, 130.04, 124.60, 123.14, 122.63,
114.34, 63.60, 30.95, 14.51.
2-(4-Iodobenzoylamino)-5-(1-phenyl-1H-tetrazole-5-
ylthiolmethylene)-1,3,4-thiadiazole (4i)
Yield 78%, m.p. 229–230◦C IR(KBr) υ (cm−1): 3167, 1671, 1587, 1390,
1310, 689. Anal. calc. for C17H12OS2N7I: C, 39.16; H, 2.32; N, 18.81.
1
Found: C, 38.95; H, 2.09; N, 18.89. H NMR(DMSO-d6): δ = 13.11(s,
1H, NH ), 7.57–7.92 (m, 9H, Ar-H), 4.98 (s, 2H, SCH2 ).
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