Synthesis of some novel 1,3,4- and 1,2,4-thiadiazole derivatives

Article abstract of DOI:10.1080/10426500802625453

Synthesis and spectral characterization of novel 1,3,4-thiadiazole derivatives including one organo-mercury compound are described. Their structure elucidation was performed by means of spectroscopic and physical methods (IR, ¹H NMR, ¹³

Full text of DOI:10.1080/10426500802625453

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Phosphorus, Sulfur, and Silicon
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Synthesis of Some Novel
1,3,4- and 1,2,4-Thiadiazole
Derivatives
Yaşar Dürüst a
a Department of Chemistry , Abant İzzet Baysal
University , Bolu, Turkey
Published online: 03 Nov 2009.
To cite this article: Yaşar Dürüst (2009) Synthesis of Some Novel 1,3,4- and 1,2,4-
Thiadiazole Derivatives, Phosphorus, Sulfur, and Silicon and the Related Elements,
184:11, 2923-2935, DOI: 10.1080/10426500802625453
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Phosphorus, Sulfur, and Silicon, 184:2923–2935, 2009
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500802625453
Synthesis of Some Novel 1,3,4- and 1,2,4-Thiadiazole
Derivatives
¨ ¨
Yas¸ar Durust
˙
Department of Chemistry, Abant Izzet Baysal University, Bolu, Turkey
Synthesis and spectral characterization of novel 1,3,4-thiadiazole derivatives in-
cluding one organo-mercury compound are described. Their structure elucidation
was performed by means of spectroscopic and physical methods (IR, 1H NMR, 13
NMR, MS, X-ray).
C
Keywords Oxadiazole; spectroscopy; thiadiazole; thione
INTRODUCTION
Heterocyclic compounds are commonly used scaffolds on which phar-
macophores are arranged to provide potent and selective drugs.1 This is
especially true for five-membered ring heterocyclic compounds, which
serve as the core components of a large number of substances that
possess a wide range of interesting biological activities. In this fam-
ily, 1,3,4-oxadiazoles and 1,3,4-thiadiazoles have been used as starting
compounds to produce substances of interest in numerous therapeutic
areas, such as antiimflammatory,2 antimicrobial,3 anticonvulsant,4 and
antihypertensive.5 In addition, these heterocycles serve as intermedi-
ates in the preparation of various biologically important compounds
and as optical materials.6,7
In this article, the synthesis and characterization of some new 1,3,4-
and 1,2,4-thiadiazole derivatives is reported.
Received 8 July 2008; accepted 13 November 2008.
Dr. F. R. Fronczek (Louisiana State University, Baton Rouge, Louisiana, USA) is
gratefully acknowledged for X-ray data of compound 7. CCDC data Durust21 contains
the supplementary crystallographic data for 7. These data can be obtained free of charge
via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallo-
graphic Data Center, 12 Union Road, Cambridge CB2 1EZ, UK; fax:+44 1223–336-033;
or email: depositcdc@cam.ac.uk.
˙
Address correspondence to Yas¸ar Du¨ru¨st, Department of Chemistry, Abant Izzet
Baysal University, TR-14280, Bolu, Turkey. E-mail: yasardurust@ibu.edu.tr
2923

2924
Y. Du¨ ru¨st
RESULTS AND DISCUSSION
In our previous work, we have been involved in the synthesis of
thiadiazole derivatives, which were essentially prepared from ami-
doximes.8,9 In this study, as starting compounds, 5-mercapto-3-phenyl-
1,3,4-thiadiazole-2(3H)-thione (potassium salt) 1,10 1,3,4-thiadiazole-
2,5-dithiol 4, and 3-(4-methyphenyl)-1,2,4-thiadiazole-5(4H)-thione 6
were utilized to react with aryl chlorides to prepare the new thiadi-
azoles. The reactions are the type of S-arylation of the heterocyclic
thiones,11 and the products are the first examples carrying 1,2,4-
oxadiazole moiety along with the 1,3,4-thiadiazole ring. The structures
of the new compounds are shown in Schemes 1–3.
SCHEME 1

Novel 1,3,4- and 1,2,4-Thiadiazole Derivatives
2925
SCHEME 2
In addition, a new organo-mercury compound 8 was also obtained
from the reaction between potassium 4-phenyl-5-thioxo-4,5-dihydro-
1,3,4-thiadiazole-2-thiolate 110 and mercury (II) chloride at refluxing
temperature in ethanol (Scheme 4) and characterized by spectral and
physical data. The mass spectrum of the compound revealed that loss
of mercury would produce peaks related to the disulfide species with
m/z (452) and mercury cation with m/z (202).12
The S-arylated compound 7 was obtained by a slightly modified lit-
erature procedure9 with a higher yield of reaction and more spectral
data for this compound were provided herein. The X-ray view of 7 is
illustrated in Figure 1. The following software programs were used:

2926
Y. Du¨ ru¨st
SCHEME 3
data collection: COLLECT13; cell refinement: SCALEPACK14; data re-
duction: DENZO14 and SCALEPACK; programs used to solve struc-
ture: SIR971; programs used to refine structure: SHELX9716; molecular
graphics: ORTEP-3 for Windows17; software used to prepare material
for publication: SHELXL97 (Tables I and II).
The S1-C1 distance (1.765 Å) is indicative of a single bond, which
is in accord with the mean value of 1.761 Å reported for arene thio-
lates18 and slightly longer than that of mercury thiolate (1.749 Å).12 The
SCHEME 4

Novel 1,3,4- and 1,2,4-Thiadiazole Derivatives
2927
FIGURE 1 ORTEP view of 7.
S2-N2 distance (1.6425 Å) is somewhat shorter than that of 3-
methylthio 5-chloro 1,2,4-thiadiazole (1.6629 Å).19 Bond distances and
bond angles within the 1,2,4-thiadiazole ring are consistent with those
of our previous report.12
EXPERIMENTAL
1H and 13C NMR spectra were recorded on Bruker and Varıan spec-
trometers (300 and 400 MHz for proton, 75 and 100 MHz for carbon).
IR spectra were recorded on Jasco 430 FTIR and Shimadzu FTIR-
8000S instruments (KBr pellet). Mass spectra were measured on an
Agilent GC 6890N gas chromatograph with mass detector MS 5975.
Melting points were determined on a Meltemp apparatus and are un-
corrected. Flash column chromatography was performed using silica
gel (Merck, 230–400 mesh ASTM). TLC was performed using precoated
plates with fluorescent indicator (Merck 5735). The stain solutions of
permanganate, p-anisaldehyde, and iodine were used for visualization
of the TLC spots.
1,3,4-thiadiazole-2,5-dithiol 4 was purchased from Aldrich and used
without purification. 5-Chloromethyl-3-phenyl-1,2,4-oxadiazole 2a,

2928
Y. Du¨ ru¨st
TABLE I Crystal Data of 7
C15H10N4O4S2
Mr = 374.39
Triclinic
V = 761.0 (4) Å3
Z = 2
Dx = 1.634 Mg m−3
Dm not measured
Mo Kα radiation
ꢀ = 0.71073 Å
Cell parameters from 2765
reflections
¯
PI
a = 4.4874 (15) Å
b = 11.497 (4) Å
c = 15.154 (5) Å
α = 101.160 (16)◦
θ = 2.5–29.8◦
β = 95.41 (2)◦
µ = 0.381 mm−1
γ = 93.61 (2)◦
T = 110 K
Tmin = 0.853, Tmax = 0.970
9387 measured reflections
4076 independent reflections
2956 reflections with I > 2σ(I)
Rint = 0.035
Needle
Yellow
0.43 × 0.12 × 0.08 mm
Data collection
Nonius KappaCCD (with Oxford
Cryostream) diffractometer
ω scans with κ offsets
Absorption correction:
multi-scan HKL Scalepack (Otwinowski
& Minor 1997)
θ
= 29.8◦
max
h = −6 → 6
k = −15 → 15
l = -21 → 21
intensity decay: <2%
2
Refinement
where P = (Fo + 2Fc2)/3
Refinement on F2
R[F2 > 2 σ(F2)] = 0.044
ωR(F2) = 0.103
S = 1.021
(
/σ)max = 0.001
ρ
= 0.69 e Å−3
ρ
max = −0.52 e Å−3
min
Extinction correction: SHELXL
Extinction coefficient: 0.005 (2)
Scattering factors from
4076 reflections
228 parameters
International Tables
H-atom parameters constrained
for Crystallography (Vol. C)
ω = 1/[σ2(Fo2) + (0.0385P)2 + 0.4038P]
5-(chloromethyl)-3-p-tolyl-1,2,4-oxadiazole 2b, and potassium 4-
phenyl-5-thioxo-4,5-dihydro-1,3,4-thiadiazole-2-thiolate 1 were syn-
thesized according to the procedures previously described in the lit-
erature.89
3-Phenyl-5-{(3-phenyl-1,2,4-oxadiazol-5-yl)methylthio}-1,3,4-
thiadiazole-2(3H)-thione (3a)
5-Chloromethyl-3-phenyl-1,2,4-oxadiazole 2a8 (1 mmol) in THF (5 mL)
was added dropwise to potassium 4-phenyl-5-thioxo-4,5-dihydro-1,3,4-
thiadiazole-2-thiolate 110 (1 mmol) in THF (5 mL). A yellow solution

Novel 1,3,4- and 1,2,4-Thiadiazole Derivatives
2929
TABLE II Selected Geometric Parameters (Å, ◦)
Bond lengths
O4—N4 1.224 (2)
S1—C1 1.765 (2)
S1—C10 1.767 (2)
S2—N2 1.6425 (18)
S2—C1 1.716 (2)
O1—N3 1.227 (2)
O2—N3 1.228 (2)
O3—N4 1.227 (3)
N1—C1 1.315 (3)
N1—C2 1.384 (3)
N2—C2 1.327 (3)
N3—C11 1.470 (3)
N4—C13 1.466 (3)
C2—C3 1.473 (3)
C6—C9 1.508 (3)
Bond Angles
C1—S1—C10 104.51 (9)
N2—S2—C1 92.04 (10)
C1—N1—C2 108.01 (17)
C2—N2—S2 108.97 (14)
N1—C1—S2 112.85 (15)
N1—C1—S1 128.94 (15)
S2—C1—S1 117.86 (12)
N2—C2—N1 118.10 (18)
N2—C2—C3 121.42 (18)
N1—C2—C3 120.48 (17)
C15—C10—S1 122.68 (15)
C11—C10—S1 120.81 (15)
C1—S2—N2—C2 −1.30 (14)
C2—N1—C1—S2 0.3 (2)
C2—N1—C1—S1 173.29 (15)
N2—S2—C1—N1 0.58 (15)
N2—S2—C1—S1 −173.25 (12)
C10—S1—C1—N1 51.0 (2)
C10—S1—C1—S2 −136.28 (12)
S2—N2—C2—N1 1.8 (2)
S2—N2—C2—C3 −178.89 (15)
C1—N1—C2—N2 −1.4 (2)
C1—N1—C2—C3 179.31 (17)
N2—C2—C3—C8 166.56 (19)
N1—C2—C3—C8 −14.2 (3)
N2—C2—C3—C4 −13.1 (3)
N1—C2—C3—C4 166.18 (18)
C1—S1—C10—C15 −14.00 (19)
C1—S1—C10—C11 166.05 (16)
S1—C10—C11—C12 −179.51 (16)
S1—C10—C11—N3 −0.2 (3)
S1—C10—C15—C14 −179.75 (17)
appeared. The reaction mixture was stirred at room temperature for 1
day. A white precipitate that formed (KCl) was filtered off. The solvent
was removed under reduced pressure. The crude product was crystal-
lized from benzene as pale yellow needles to give compound 3a (400 mg,
78%), mp 84–85◦C. Rf : 0.57 (ethanol:n-hexane, 3:1). IR (KBr) v (cm−1):
1591, 1566, 1492, 1444, 1359, 1228. 1H NMR (CDCl3, 400 MHz): δ: 8.09
(d, 2H, J = 6.1 Hz), 7.63 (d, 2H, J = 3.7 Hz), 7.55–7.39 (m, 6H), 4.58
(s,2H).13C NMR (CDCl3, 100 MHz).: 185.6 (C = S), 174.2,168.7, 151.9,
138.2, 131.4, 128.9, 128.8, 127.5, 126.2, 125.3, 96.1, 26.7.MS (m/z,%):
383 (M+, 44), 135 (14), 105 (31), 77 (100), 64 (13), 51 (16). Anal. Calcd
for C17H12N4OS3 :C, 53.10; H, 3.15; N, 14.57; S, 25.02.Found. 53.39; H,
3.01; N,14.50; S,25.90.
3-Phenyl-5-{(3-p-tolyl-1,2,4-oxadiazol-5-yl)methylthio}-1,3,4-
thiadiazole-2(3H)-thione (3b)
5-Chloromethyl-3-p-tolyl-1,2,4-oxadiazole 2b8 (1 mmol) in THF (5
mL) was added to potassium 4-phenyl-5-thioxo-4,5-dihydro-1,3,4-

2930
Y. Du¨ ru¨st
thiadiazole-2-thiolate 110 (1mmol) in THF (5 mL). A yellow solution
appeared. The reaction mixture was stirred at room temperature for
3 days. A white precipitate that formed (KCl) was filtered off. The
solvent was removed under reduced pressure. The crude product was
crystallized from hexane as white flocculent crystals to give compound
3b (quantitative). Mp 84–86◦C. Rf: 0.67 (EtOAc:hexane, 1:3). IR (KBr)
1
v (cm−1):1590, 1494, 1227, 1041. H NMR (CDCl3, 400 MHz): δ: 7.98
(d, 2H, J = 8.4 Hz), 7.67 (d, 2H, J = 8.0 Hz), 7.42 (m, 3H), 7.29 (m,
2H), 4.66 (s, 2H), 2.45 (s, 3H). 13C NMR (CDCl3, 100 MHz): δ: 185.6
(C=S), 174.0, 168.6, 151.9, 141.6, 138.2, 129.6, 128.8, 127.4, 125.3,
123.4, 96.1, 26.7, 21.6. MS (m/z,%): 397 (M+, 97), 135 (18), 117 (10),
105 (49), 91 (35), 77 (100), 64 (13), 51 (18). Anal.Calcd for C18H14N4OS3
C, 54.25; H, 3.54; N, 14.06; S, 24.14.Found. C,54.67;H, 4.07; N, 14.01; S,
25.19.
5-(2,4-Dinitrophenylthio)-3-phenyl-1,3,4-thiadiazole-2(3H)-
thione (3c)
1-Chloro-2,4-dinitrobenzene 2c (303 mg, 1.5 mmol) in THF (5 mL) was
added to potassium 4-phenyl-5-thioxo-4,5-dihydro-1,3,4-thiadiazole-2-
thiolate 110 (396 mg, 1.5 mmol) in THF (5 mL). The reaction mixture
was stirred at room temperature for 1 day. The reaction mixture was
was taken into water and extracted with CH2Cl2 (3 × 25 mL) and dried
over Na2SO4. The solvent was removed under reduced pressure. The
crude product was crystallized from hexane as pale yellow needles to
give compound 3c (quantitative). Mp 173–175◦C. Rf: 0.24 (ethanol:n-
hexane, 2:1). IR (KBr) v, (cm−1):1600, 1535, 1337, 1223, 1025, 908, 730.
1H NMR (CDCl3, 400 MHz): δ: 9.64 (s, 1H), 8.59 (s, 1H), 7.70 (m, 6H).
13C NMR (CDCl3, 100 MHz): δ:188.4, 147.4, 146.2, 145.3, 140.4, 137.6,
129.7, 129.2, 128.0, 125.6, 121.6. MS (m/z,%): 391 (M+,20), 183 (13), 135
(17), 77 (100), 64 (22), 51 (16). Anal. Calcd for C14H8N4O4S3: C, 42.85;
H, 2.05; N, 14.28; S, 24.51. Found C,43.47;H,2.02; N, 14.24; S, 26.21.
5-(Naphthalen-1-ylmethylthio)-3-phenyl-1,3,4-thiadiazole-
2(3H)-thione (3d)
1-Chloromethyl naphthalene 2d (110.5 mg, 0.5 mmol) in THF (5
mL) was added to potassium 4-phenyl-5-thioxo-4,5-dihydro-1,3,4-
thiadiazole-2-thiolate 110 (133 mg, 0.5 mmol) in THF (5 mL). The reac-
tion mixture was stirred at room temperature for 2 h. The solvent
was evaporated, and the crude material was crystallized from
petroleum ether as white flocculent plates to give compound 3d (151 mg,

Novel 1,3,4- and 1,2,4-Thiadiazole Derivatives
2931
41%). Mp 100–101◦C. Rf: 0.96 (n-hexane:ethyl acetate, 2:1). IR (KBr) v
1
(cm−1):1594, 1495, 1342, 1245, 1050, 820, 744, 683. H NMR (CDCl3,
400 MHz): δ: 7.88–7.46 (m, 12H), 4.48 (s, 2H). 13C NMR (CDCl3, 100
MHz): δ:185.9, 155.2, 138.4, 133.1, 132.9, 132.32, 129.0, 128.9, 128.8,
128.5, 127.8, 127.7, 126.6, 126.5, 126.5, 125.6, 37.8. MS (m/z,%): 365
(M+,5), 141 (100), 115 (20), 77 (14), 64 (3), 51 (13). Calculated for
C19H14N2S3 C, 62.26; H, 3.85; N, 7.64; S, 26.25 Found C, 62.84; H,
4.40; N, 7.67; S, 26.96.
3-Phenyl-5-{(5-((3-phenyl-1,2,4-oxadiazol-5-yl)methylthio}-
1,3,4-thiadiazol-2-ylthio)methyl)-1,2,4-oxadiazole (5a)
5-(Chloromethyl)-3-phenyl-1,2,4-oxadiazole 2a8 (260 mg, 1.34 mmol) in
THF (5 mL) was added dropwise into a solution of 1,3,4-thiadiazole-2,5-
dithiol 4 (100 mg, 0.67mmol) in EtOH (5 mL) containing KOH (75 mg,
1.34 mmol) and stirred at room temperature for 1 day. The mixture
was evaporated to dryness. The yellow solid was taken into the water
(50 mL) and extracted with CH2Cl2 (3 × 20 mL). The combined organic
fractions were dried over anhydrous Na2SO4, and after evaporation of
the solvent, the remaining solid was crystallized from EtOH to give 5a
(0.211 g, 67.1%). Mp 103–105◦C. IR (KBr) v (cm−1): 1592, 1568, 1446,
1385, 1359, 1049, 908, 713, 687. 1H NMR (DMSO-d6, 400 MHz): δ: 8.11
(m, 4H), 7.75 (m, 6H), 4.96 (s, 4H). 13C NMR (DMSO-d6, 100 MHz)
δ: 189.2, 176.9, 168.3, 164.6, 155.8, 132.6, 1342.2, 132.1, 129.7, 128.7,
127.4, 126.3, 126.2, 28.4, 127.9. MS (m/z,%): 466 (M+, 10), 307 (16), 191
(9), 159 (23), 145 (24), 129 (96), 103 (100), 91 (37), 76 (74), 64 (45), 51
(62). Calculated for C20H14N6O2S3.H2O C, 49.57; H, 3.33; N, 17.34; S,
19.85. Found C, 49.36; H, 3.60; N, 17.69; S, 20.01.
3-o-Tolyl-5-{(5-(3-o-tolyl-1,2,4-oxadiazol-5-yl)methylthio)-1,3,4-
thiadiazol-2-ylthio)methyl}-1,2,4-oxadiazole (5b)
5-(Chloromethyl)-3-p-tolyl-1,2,4-oxadiazole 2b8 (490 mg, 2.40 mmol) in
THF (5 mL) was added dropwise into a solution of 1,3,4-thiadiazole-
2,5-dithiol 4 (180 mg, 1.20 mmol) in EtOH (5 mL) containing NaOH
(96 mg, 2.40 mmol) and stirred at room temperature for 1 day. The
mixture was evaporated to dryness and extracted with ethyl acetate.
NaCl was filtered off. The crude reaction product was crystallized from
petroleum ether to give 5b (679 mg, 77%). Mp 98–100◦C. IR (KBr) v
(cm−1): 1594, 1592, 1567, 1560, 1345, 1051, 905, 902, 739, 726. 1H NMR
(DMSO-d6, 400 MHz): δ: 8.11 (m, 4H), 7.75 (m, 6H), 4.96 (s, 4H). 13C
NMR (DMSO-d6, 100 MHz) δ: 173.6, 169.3, 163.3, 138.3, 131.4, 130.8,

2932
Y. Du¨ ru¨st
130.1, 126.0, 125.5, 27.8, 22.1. MS (m/z,%): 321 (M+-173, 6), 159 (100),
131 (27), 116 (48), 104 (10), 89 (22), 77 (23), 63 (14), 51 (9). Calculated
for C22H18N6O2S3 C, 53.42; H, 3.67; N, 16.99; S, 19.45 Found C, 53.12;
H, 3.63; N,16.76; S,19.45.
2,5-Bis(naphthalen-1-ylmethylthio)-1,3,4-thiadiazole (5c)
A mixture of 2,5-dimercapto-1,3,4-thiadiazole 4 (150.2 mg, 1 mmol)
in an aqueous solution of NaOH (80 mg, 2 mmol) and 1-chloromethyl
naphthalene (442 mg, 2 mmol) was stirred at room temperature
overnight. The solvent was evaporated to dryness. The remaining solid
was extracted with benzene, then successively with ethyl acetate and
ethanol. The combined organic fractions were evaporated, and the re-
maining solid was finally crystallized from benzene-petroleum ether
(50–70◦C) to give 5c as flocculent shiny plates (370 mg, 86%). Mp
1
131–133◦C. IR (KBr) v (cm−1): 1594, 1505, 1383, 1051, 831, 752. H
NMR (CDCl3, 400 MHz): δ:7.86–7.80 (m, 8H), 7.53–7.49 (m, 6H), 4.42
(s, 4H). 13C NMR (CDCl3, 100 MHz) δ: 164.7, 133.2, 133.1, 132.8, 128.6,
128.2, 127.8, 127.7, 126.8, 126.4, 126.3, 38.7. MS (m/z,%): 430 (M+, 9),
396 (6), 198 (9), 141 (100), 115 (24). Anal Calcd for C24H18N2S3 C, 66.94;
H, 4.21; N, 6.51; S, 22.34.Found. C,67.13;H,3.77;N,6.50; S,22.38.
2,5-Bis(2,4-dinitrophenylthio)-1,3,4-thiadiazole (5d)
An aqueous alcoholic solution of 2,5-dimercapto-1,3,4-thiadiazole 4 (225
mg, 1.5 mmol), NaOH (120 mg, 3 mmol), and 2,4-dinitro chloro benzene
(607 mg, 3 mmol) was mixed and stirred at room temperature overnight.
The reaction mixture was evaporated to dryness, and the remaining
material was taken into water (50 mL). The pale yellow precipitate
was filtered and crystallized from ethanol as a pale yellow powder 5d.
Mp 236–237◦C (710 mg, 98%).Rf:0.35 (EtOAc:n-hexane, 1:2) IR (KBr) v
(cm−1): 1591, 1516, 1346, 1049, 833, 736. 1H NMR (DMSO-d6 +CDCl3,
400 MHz):δ: 8.96 (d, J = 2.4 Hz, 2H), 8.44 (dd, J = 8.9 2.5 Hz, 2H),
8.23 (s, 1H), 7.67 (d, J = 2.4 Hz, 2H). 13C NMR (DMSO-d6+ CDCl3, 100
MHz):δ: 165.0, 146.2, 131.4, 128.8, 121.5. MS (m/z,%): 436 (M+, 17), 183
(58), 137 (100), 95 (63), 63 (76), 51 (14). Calculated for C14H6N6O8S3
C, 34.85; H, 1.25; N, 17.42; S, 19.94. Found. 35.16; H, 1.37; N, 17.39; S,
19.56.
(2,4-Dinitrophenylthio)-3-(4-methylphenyl)-1,2,4-thiadiazole
(7)
To a stirring solution of 3-(4-methyphenyl)-1,2,4-thiadiazole-5(4H)-
thione 6 (208 mg,1 mmol) in N,N-dimethylformamide (10 mL) at room

Novel 1,3,4- and 1,2,4-Thiadiazole Derivatives
2933
temperature, potassium tert-butoxide (120 mg, 1 mmol) was added. Af-
ter stirring for 25 min, 2,4-dinitrochlorobenzene (202 mg, 1 mmol) in
N,N-dimethylformamide (5 mL) was added, and the reaction mixture
was stirred for further 24 h at room temperature. After the disappear-
ance of the starting materials (TLC monitoring), the reaction mixture
was quenched with brine (50 mL) and extracted with dichloromethane
(3 × 30 mL). The combined organic fractions were dried over MgSO4,
filtered, and concentrated under reduced pressure. Crystallization from
benzene:petroleum ether (1:1) gave 7 as yellow needles. Mp 169–171◦C
(Lit.11 168–170◦C) (82%). 13C NMR (CDCl3, 100 MHz) δ: 178.8, 175.0,
146.0, 145.6, 141.7, 140.1, 130.8, 129.1, 128.3, 127.6, 121.3, 21.5. MS
(m/z,%): 374 (M+, 35), 328 (7), 149 (100), 117 (32), 91 (13), 63 (6).
3-Phenyl-5-{(4-phenyl-5-thioxo-4,5-dihydro-1,3,4-thiadiazol-2-
ylthio)mercuriothio}-1,3,4-thiadiazole-2(3H)-thione (8)
An aqueous ethanolic solution of mercury (II) chloride (197 mg, 0.5
mmol) (10 mL) was added dropwise to a solution of potassium 4-phenyl-
5-thioxo-4,5-dihydro-1,3,4-thiadiazole-2-thiolate 110 (264 mg, 1 mmol)
in ethanol (5 mL). The reaction mixture was refluxed for 2 h. The solvent
was removed under reduced pressure. The remaining solid material
was dissolved in THF and filtered to remove solid parts (KCl). After the
evaporation of solvent, crude material was crystallized from ethanol to
give 8 as yellow powder (0.435 g, 65%). Mp 186–187◦C. IR (KBr) v
(cm−1): 1628 (C=N), 1492, 1429, 1365, 1230, 1020, 842, 759, 682, 607.
1H NMR (DMSO-d6, 400 MHz): δ: 7.95–7.58 (m, 4H), 7.58–7.25 (m,
6H).13C NMR (DMSO-d6, 100 MHz) δ: 186.9 (C=S), 159.7, 138.4, 129.4,
126.0.MS (m/z,%): 450 (M-Hg, 9), 314 (4), 226 (9), 202 (6), 135 (36), 105
(28), 77 (100), 63 (95), 51 (26). Calculated for C16H10HgN4S6 C, 29.51;
H, 1.55; N, 8.60; S, 29.54 found C, 30.14; H, 1.66; N, 8.55; S, 29.08.
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