Synthesis of 2-amino-5-mercapto-1,3,4-thiadiazole derivatives

Article abstract of DOI:10.1515/hc-2013-0212

2-Amino-5-mercapto-1,3,4-thiadiazole (AMT) was used to synthesize 24 new compounds. The structures were confirmed by ¹H NMR and ¹³C NMR.

Full text of DOI:10.1515/hc-2013-0212

ꢁꢁꢁꢂ
ꢀHeterocycl. Commun. 2014; 20(1): 33–36
DOI 10.1515/hc-2013-0212ꢀ
Wen-You Li*, Yong Song, Hong-Bo Chen and Wen-Long Yang
Synthesis of 2-amino-5-mercapto-1,3,4-
thiadiazole derivatives
Abstract: 2-Amino-5-mercapto-1,3,4-thiadiazole (AMT) DMSO, water, and MeOH. The results indicated that MeOH
was used to synthesize 24 new compounds. The structures is the optimal solvent. The reaction hardly proceeded in
were confirmed by 1H NMR and 13C NMR.
the remaining solvents. The highest yields of 1a and 2a
were obtained in the presence of triethylamine, lower
Keywords: 2-amino-5-mercapto-1,3,4-thiadiazole; chloro- yields were obtained in the presence of EtONa, and no
acetyl chloride; heterocyclic.
products were detected in the attempted reactions in the
presence of NaOH or NaHCO3. Products 1b,c and 2b,c were
prepared in a similar manner by subjecting AMT to the
Michael addition with methyl acrylate and butyl acrylate
(Scheme 1).
Then, our attention focused on the acylation reaction
of 1a–c and 2a–c with chloroacetyl chloride, which yielded
the respective derivatives 3a–c and 4a–c. These products
were cyclized to two different rings by the reaction with
potassium isothiocyanate. The imidazole derivatives 5a–c
and 7a–c are formed in the reaction with KSCN conducted
in acetonitrile, and the thiazole derivatives 6a–c and 8a–c
are obtained in DMF at 80°C. A unified mechanism that
accounts for these two different outcomes is proposed in
Scheme 2.
*Corresponding author: Wen-You Li, Dalian University of
Technology, Dalian 116012, P.R. China; and Department of Chemical
Engineering, Jiuquan Vocational and Technical College, Jiuquan
735000, P.R. China, e-mail: jqzylwy@163.com
Yong Song and Hong-Bo Chen: Dalian University of Technology,
Dalian 116012, P.R. China
Wen-Long Yang: Department of Chemical Engineering, Jiuquan
Vocational and Technical College, Jiuquan 735000, P.R. China
Introduction
Recent drug studies are highly focused on heterocy-
clic ring systems. Thiadiazoles are one of the privileged
structural fragments. Fused systems containing the thia-
diazole ring give rise to compounds with varied bioac-
tivities, such as anticancer [1], antimicrobial [2, 3], and
antiviral [4] properties. Currently, compounds A [5] and
B [6, 7] (Figure 1) are in clinical trials, and several other
1,3,4-thiadiazole derivatives including C [8, 9], D [10],
and the parent compound 2-amino-5-mercapto-1,3,4-
thiadiazole (AMT) [11–15] display a variety of biological
activities. Several synthetic strategies to AMT have been
reported [16]. The easy accessibility of AMT prompted us
to prepare a new series of 2-amino-5-mercapto-1,3,4-thia-
diazole derivatives.
H
N
S
S
N
Se
S
N
R
R
N
H O
N
N
OH
O
A
B
H
N
O
S
S
Cl
R
O
N
N
C
Results and discussion
MeO
N
N
O2N
COOH
S
N
O
First, the Michael addition reaction of AMT with α,β-
unsaturated compounds was studied. With acrylonitrile
as the substrate, the products 1a and 2a were obtained in
the respective yields of 47% and 49% under optimal con-
ditions. This reaction was studied using EtOH, acetone,
N
N
O
F
D
Figure 1ꢀSelected biologically active 1,3,4-thiadiazole derivatives.
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34ꢀ ꢀW.-Y. Li et al.: 2-Amino-5-mercapto-1,3,4-thiadiazoles
R
N
N
N
N
N N
R
R
H2N
SH
H2N
S
H2N
S
S
S
S
Michael addition
1a-c
2a-c
ClCH2COCl
Cl
R
Cl
N
N
N
N
R
O
O
S
N
H
S
N
S
S
H
3a-c
4a-c
KSCN
KSCN
R
O
O
O
O
N
N
S
N
N
R
R
NH
NH
N
N
N
S
S
N
N
N
R
S
S
HN
S
HN
S
N
N
S
S
S
S
S
5a-c
6a-c
7a-c
8a-c
a: R = CN; b: R = COOMe; c: R=COOBun
Scheme 1ꢀ
heated under reflux for 4–8 h. Afer cooling, the mixture was concen-
trated under reduced pressure, and the residue was purified by silica
gel chromatography eluting with dichloromethane/methanol (95:5)
to give starting AMT followed by the products 1a–c and 2a–c.
KSCN = K + SCN
S
C N
S
C
N
H
O
O
H
N
O
N
R
R
O
R
C
S
S
C
C
N
N
N
R
3-(5-Amino-2-thioxo-1,3,4-thiadiazol-3(2H)-yl)propanenitrile
(1a)ꢀYield 47%; mp 103–105°C; IR (cm-1): 3415, 3284, 2173, 1619, 1553,
S
N
H
Cl
N
S
1
1182, 1066; H NMR (CDCl3): δ 3.04 (t, J ꢀ= ꢀ 7 Hz, 2H), 4.41 (t, J ꢀ= ꢀ 7 Hz,
2H), 6.68 (s, 2H). Anal. Calcd for C5H6N4S2: C, 32.24; H, 3.25; N, 30.08;
S, 34.43. Found: C, 32.22; H, 3.26; N, 30.07; S, 34.45.
H
N
H
N
O
NH
O
R
Methyl 3-(5-amino-2-thioxo-1,3,4-thiadiazol-3(2H)-yl)propanoate
(1b)ꢀYield 29%; mp 119–121°C; IR (cm-1): 3416, 3285, 2924, 1718, 1620,
1556, 1213, 1068; 1H NMR (CDCl3): δ 2.82 (t, J ꢀ= ꢀ 7 Hz, 2H), 3.64 (s, 3H),
4.36 (t, J ꢀ= ꢀ 7 Hz, 2H), 6.60 (s, 2H). Anal. Calcd for C6H9N3O2S2: C, 32.86;
H, 4.14; N, 19.16; O, 14.59; S, 29.25. Found: C, 32.88; H, 4.13; N, 19.18; O,
14.57; S, 29.23.
N
R
N
S
C
Cl
S
Scheme 2ꢀ
Experimental
Butyl 3-(5-amino-2-thioxo-1,3,4-thiadiazol-3(2H)-yl)propanoate
(1c)ꢀYield 17%; red brown foam; IR (cm-1): 3315, 3191, 2959, 1724,
1559, 1256, 1184, 1068; 1H NMR (CDCl3): δ 0.92 (t, J ꢀ= ꢀ 8 Hz, 3H), 1.41 (m,
J ꢀ= ꢀ 8 Hz, 2H), 1.61 (m, J ꢀ= ꢀ 8 Hz, 2H), 2.83 (t, J ꢀ= ꢀ 8 Hz, 2H), 4.07 (t, J ꢀ= ꢀ 8
Hz, 2H), 4.37 (t, J ꢀ= ꢀ 8 Hz, 2H), 6.55 (s, 2H). Anal. Calcd for C9H15N3O2S2:
C, 41.36; H, 5.78; N, 16.08; O, 12.24; S, 24.54. Found: C, 41.37; H, 5.76;
N, 16.06; O, 12.23; S, 24.56.
General
Melting points were determined on a Perkin-Elmer differential scan-
ning calorimeter and are uncorrected. The IR spectra were run on a
Nicolete spectrometer using KBr pellets. NMR spectra were recorded
at 400 MHz (1H) and 100 MHz (13C) on a Varian Mercury plus-400
instrument.
3-[(5-Amino-1,3,4-thiadiazol-2-yl)thio]propanenitrile (2a)ꢀYield
49%; mp 136–137°C; IR (cm-1): 3297, 3102, 2170, 1631, 1579, 1504, 1068;
1H NMR (CDCl3): δ 2.93 (t, J ꢀ= ꢀ 7 Hz, 2H), 3.33 (t, J ꢀ= ꢀ 7 Hz, 2H), 7.38 (s,
2H). Anal. Calcd for C5H6N4S2: C, 32.24; H, 3.25; N, 30.08; S, 34.43.
Found: C, 32.25; H, 3.27; N, 30.09; S, 34.44.
General procedure for synthesis of
compounds 1a–c and 2a–c
Triethylamine (0.6 mL, 0.86 mmol) was slowly added to a solution of
AMT (0.66 g, 5 mmol), acrylonitrile, methyl acrylate or butyl acrylate
(2 mmol) in CH3OH (50 mL) under nitrogen, and the mixture was
Methyl 2-[(5-amino-1,3,4-thiadiazol-2-yl)thio]propanoate (2b)ꢀ
Yield 58%; mp 102–104°C, IR (cm-1): 3311, 3101, 2926, 1728, 1633, 1503,
1
1246, 1066; H NMR (CDCl3): δ 2.81 (t, J ꢀ= ꢀ 7 Hz, 2H), 3.34 (t, J ꢀ= ꢀ 7 Hz,
2H), 3.65 (s, 3H), 6.64 (s, 2H). Anal. Calcd for C6H9N3O2S2: C, 32.86; H,
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W.-Y. Li et al.: 2-Amino-5-mercapto-1,3,4-thiadiazolesꢀ
ꢀ35
4.14; N, 19.16; O, 14.59; S, 29.25. Found: C, 32.85; H, 4.16; N, 19.17; O, 0.66 mmol) and the mixture was stirred for 15 min at room tempera-
14.60; S, 29.26.
ture. Afer addition of KSCN (0.1 g, 1 mmol), the mixture was heated
to 80°C for 1 h, then cooled and concentrated under reduced pres-
Butyl 2-[(5-amino-1,3,4-thiadiazol-2-yl)thio]propanoate (2c)ꢀYield sure. The residue was purified by silica gel chromatography eluting
42%; mp 93–95°C, IR (cm-1): 3298, 3102, 2958, 1723, 1502, 1247, 1066; 1H with dichloromethane/methanol (95:5).
NMR (CDCl3): δ 0.92 (t, J ꢀ= ꢀ 7 Hz, 3H), 1.38 (m, J ꢀ= ꢀ 7 Hz, 2H), 1.58 (m, J ꢀ= ꢀ 7
Hz, 2H), 2.80 (t, J ꢀ= ꢀ 7 Hz, 2H), 3.34 (t, J ꢀ= ꢀ 7 Hz, 2H), 4.08 (t, J ꢀ= ꢀ 7 Hz, 2H), 3-[5-(5-Oxo-2-thioxoimidazolidin-1-yl)-2-thioxo-1,3,4-thiadiazol-
6.60 (s, 2H). Anal. Calcd for C9H15N3O2S2: C, 41.36; H, 5.78; N, 16.08; O, 3(2H)-yl]propanenitrile (5a)ꢀYield 56%; mp 162°C, IR (cm-1): 3432,
1
12.24; S, 24.54. Found: C, 41.35; H, 5.79; N, 16.07; O, 12.27; S, 24.51.
2273, 1749, 1625, 1571, 1175, 1083; H NMR (CDCl3): δ 3.16 (t, J ꢀ= ꢀ 7 Hz,
2H), 4.18 (s, 2H), 4.61 (t, J ꢀ= ꢀ 7 Hz, 2H), 11.05 (s, 1H). Anal. Calcd for
C8H7N5OS3: C, 33.67; H, 2.47; N, 24.54; O, 5.61; S, 33.71. Found: C, 33.69;
H, 2.45; N, 24.51; O, 5.63; S, 33.68.
General procedure for synthesis of
compounds 3a–c and 4a–c
Chloroacetyl chloride (2 mmol) was added dropwise to a stirred cold
solution (0°C) of 1a–c or 2a–c (1 mmol) in DMF (3 mL) and the mixture
was stirred at room temperature for an additional 8 h. Afer concentra-
tion under reduced pressure, the residue was crystallized from ethanol.
Methyl 3-[5-(5-oxo-2-thioxoimidazolidin-1-yl)-2-thioxo-1,3,4-thi-
adiazol-3(2H)-yl]propanoate (5b)ꢀYield 50%; mp 103–104°C, IR
(cm-1): 3420, 2922, 1738, 1582, 1251, 1184, 1078; 1H NMR (CDCl3): δ 2.95
(t, J ꢀ= ꢀ 7 Hz, 2H), 3.67 (s, 3H), 4.16 (s, 2H), 4.52 (t, J ꢀ= ꢀ 7 Hz, 2H), 10.91 (s,
1H). Anal. Calcd for C9H10N4O3S3: C, 33.95; H, 3.17; N, 17.60; O, 15.08; S,
30.21. Found: C, 33.94; H, 3.19; N, 17.59; O, 15.10; S, 30.23.
2-Chloro-N-(4-(2-cyanoethyl)-5-thioxo-4,5-dihydro-1,3,4-thia-
diazol-2-yl)acetamide (3a)ꢀYield 61%; mp 164–167°C; IR (cm-1):
3439, 2926, 2221, 1712, 1569, 1556, 1079. Anal. Calcd for C7H7ClN4OS2: C,
32.00; H, 2.69; Cl, 13.49; N, 21.32; O, 6.09; S, 24.41. Found: C, 32.02; H,
2.70; Cl, 13.50; N, 21.33; O, 6.08; S, 24.42.
Butyl 3-[5-(5-oxo-2-thioxoimidazolidin-1-yl)-2-thioxo-1,3,4-thia-
diazol-3(2H)-yl]propanoate(5c)ꢀYield43%;mp132–134°C,IR(cm-1):
3429, 2957, 1748, 1633, 1589, 1266, 1179, 1084; 1H NMR (400 MHz,
CDCl3): δ 0.93 (t, J ꢀ= ꢀ 7 Hz, 3H), 1.40 (m, J ꢀ= ꢀ 7 Hz, 2H), 1.60 (m, J ꢀ= ꢀ 7
Hz, 2H), 2.95 (t, J ꢀ= ꢀ7 Hz, 2H), 4.07 (t, J ꢀ= ꢀ 7 Hz, 2H), 4.10 (s, 2H), 4.52
(t, J ꢀ= ꢀ 7 Hz, 2H), 11.00 (s, 1H). Anal. Calcd for C12H16N4O3S3: C, 39.98;
H, 4.47; N, 15.54; O, 13.32; S, 26.69. Found: C, 39.95; H, 4.49; N, 15.55;
O, 13.30; S, 26.70.
Methyl 3-(5-(2-chloroacetamido)-2-thioxo-1,3,4-thiadiazol-3(2H)-
yl)propanoate(3b)ꢀYield: 88%; mp 112–116°C, IR (cm-1): 3441, 2917,
1710, 1691, 1582, 1212, 1183, 1075. Anal. Calcd for C8H10ClN3O3S2: C,
32.49; H, 3.41; Cl, 11.99; N, 14.21; O, 16.23; S, 21.68. Found: C, 32.50; H,
3.43; Cl, 11.97; N, 14.20; O, 16.25; S, 21.69.
3-[(5-(5-Oxo-2-thioxoimidazolidin-1-yl)-1,3,4-thiadiazol-2-yl)
thio]propanenitrile (7a)ꢀYield 67%; mp 196–198°C; IR (cm-1):
3451, 2230, 1734, 1569, 1166, 1053; 1H NMR (CDCl3): δ 3.10 (t, J ꢀ= ꢀ 7 Hz,
2H), 3.63 (t, J ꢀ= ꢀ 7 Hz, 2H), 4.11 (s, 2H), 10.90 (s, 1H). Anal. Calcd for
C8H7N5OS3: C, 33.67; H, 2.47; N, 24.54; O, 5.61; S, 33.71. Found: C, 33.68;
H, 2.49; N, 24.53; O, 5.60; S, 33.70.
Butyl 3-(5-(2-chloroacetamido)-2-thioxo-1,3,4-thiadiazol-3(2H)-yl)-
propanoate (3c)ꢀYield 87%; mp 92–94°C, IR (cm-1): 3432, 2929, 1729,
1709, 1579, 1213, 1184, 1080. Anal. Calcd for C11H16ClN3O3S2: C, 39.11; H,
4.77; Cl, 10.49; N, 12.44; O, 14.21; S, 18.98. Found: C, 39.13; H, 4.75; Cl,
10.50; N, 12.42; O, 14.23; S, 19.00.
Methyl 3-[(5-(5-oxo-2-thioxoimidazolidin-1-yl)-1,3,4-thiadiazol-
2-yl)thio]propanoate (7b)ꢀYield 75%; mp 165–167°C, IR (cm-1):
3448, 2923, 1734, 1595, 1174, 1073; 1H NMR (CDCl3): δ 2.89 (t, J ꢀ= ꢀ 7 Hz,
2H), 3.53 (t, J ꢀ= ꢀ 7 Hz, 2H), 3.67 (s, 3H), 4.10 (s, 2H), 10.90 (s, 1H). Anal.
Calcd for C9H10N4O3S3: C, 33.95; H, 3.17; N, 17.60; O, 15.08; S, 30.21.
Found: C, 33.96; H, 3.18; N, 17.61; O, 15.07; S, 30.22.
2-Chloro-N-[5-((2-cyanoethyl)thio)-1,3,4-thiadiazol-2-yl]acetamide
(4a)ꢀYield 91%; mp 174–178°C, IR (cm-1): 3439, 2925, 2230, 1707, 1582,
1065. Anal. Calcd for C7H7ClN4OS2: C, 32.00; H, 2.69; Cl, 13.49; N, 21.32; O,
6.09; S, 24.41. Found: C, 31.98; H, 2.67; Cl, 13.51; N, 21.30; O, 6.10; S, 24.43.
Methyl 3-[(5-(2-chloroacetamido)-1,3,4-thiadiazol-2-yl)thio]pro-
panoate(4b)ꢀYield 93%; mp 144–145°C, IR (cm-1): 3439, 2946, 1734,
1706, 1587, 1197, 1177, 1069. Anal. Calcd for C8H10ClN3O3S2: C, 32.49; H,
3.41; Cl, 11.99; N, 14.21; O, 16.23; S, 21.68. Found: C, 32.47; H, 3.43; Cl,
12.01; N, 14.23; O, 16.21; S, 21.67.
Butyl 3-[(5-(5-oxo-2-thioxoimidazolidin-1-yl)-1,3,4-thiadiazol-2-
yl)thio]propanoate (7c)ꢀYield 42%; mp 110–113°C, IR (cm-1): 3432,
2961, 1734, 1598, 1259, 1175, 1090; 1H NMR (CDCl3): δ 0.92 (t, J ꢀ= ꢀ 7 Hz,
3H), 1.40 (m, J ꢀ= ꢀ 7 Hz, 2H), 1.61 (m, J ꢀ= ꢀ 7 Hz, 2H), 2.89 (t, J ꢀ= ꢀ 7 Hz, 2H),
3.53 (t, J ꢀ= ꢀ 7 Hz, 2H), 4.10 (t, J ꢀ= ꢀ 7 Hz, 2H), 4.10 (s, 2H), 10.89 (s, 1H).
Anal. Calcd for C12H16N4O3S3: C, 39.98; H, 4.47; N, 15.54; O, 13.32; S,
26.69. Found: C, 39.97; H, 4.46; N, 15.57; O, 13.33; S, 26.67.
Butyl 3-((5-(2-chloroacetamido)-1,3,4-thiadiazol-2-yl)thio)pro-
panoate (4c)ꢀYield 83%; mp 105–106°C, IR (cm-1): 3435, 2961, 1729,
1704, 1577, 1296, 1183, 1065. Anal. Calcd for C11H16ClN3O3S2: C, 39.11; H,
4.77; Cl, 10.49; N, 12.44; O, 14.21; S, 18.98. Found: C, 39.10; H, 4.79; Cl,
10.51; N, 12.42; O, 14.20; S, 18.97.
General procedure for synthesis of
compounds 6a–c and 8a–c
General procedure for synthesis of
compounds 5a–c and 7a–c
A solution of 3a–c or 4a–c (1 mmol) in acetonitrile (3 mL) was treated reduced pressure, the residue was crystallized from 80% aqueous
with tetrabutylammonium bromide (TBAB, 0.1 g) and KI (0.11 g, ethanol.
A solution of 3a–c or 4a–c (1 mmol) in DMF (2 mL) was treated with
KI (0.11 g, 0.66 mmol) and KSCN (0.1 g, 1 mmol) and the mixture
was heated to 100°C for 1 h. Afer cooling and concentration under
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36ꢀ ꢀW.-Y. Li et al.: 2-Amino-5-mercapto-1,3,4-thiadiazoles
1
3-[5-((4-Oxothiazolidin-2-ylidene)amino)-2-thioxo-1,3,4-thiadi-
2933, 2245, 1735, 1651, 1561, 1168; H NMR (400 MHz, DMSO): δ 3.05
azol-3(2H)-yl]propanenitrile (6a)ꢀYield 71%; mp 206–208°C, IR
(t, J ꢀ= ꢀ 6 Hz, 2H), 3.55 (t, J ꢀ= ꢀ 6 Hz, 2H), 4.11 (s, 2H), 12.35 (s, 2H). Anal.
Calcd for C8H7N5OS3: C, 33.67; H, 2.47; N, 24.54; O, 5.61; S, 33.71. Found:
C, 33.69; H, 2.43; N, 24.57; O, 5.59; S, 33.70.
1
(cm-1): 3437, 2924, 2253, 1747, 1623, 1173, 1082; H NMR (DMSO-d6): δ
3.110 (t, J ꢀ= ꢀ 6 Hz, 2H), 4.17 (s, 2H), 4.49 (t, J ꢀ= ꢀ 6 Hz, 2H), 12.48 (s, 1H).
Anal. Calcd for C8H7N5OS3: C, 33.67; H, 2.47; N, 24.54; O, 5.61; S, 33.71.
Found: C, 33.66; H, 2.45; N, 24.55; O, 5.59; S, 33.72.
Methyl 3-[(5-((4-oxothiazolidin-2-ylidene)amino)-1,3,4-thiadia-
zol-2-yl)thio]propanoate (8b)ꢀYield 65%; mp 176–177°C, IR (cm-1):
1
Methyl 3-[5-((4-oxothiazolidin-2-ylidene)amino)-2-thioxo-1,3,4-
3430, 2924, 1732, 1597, 1251, 1173, 1071; H NMR (DMSO-d6): δ 2.85 (t,
thiadiazol-3(2H)-yl]propanoate (6b)ꢀYield 71%; mp 161°C, IR (cm-1):
J ꢀ= ꢀ 7 Hz, 2H), 3.45 (t, J ꢀ= ꢀ 7 Hz, 2H), 3.63 (s, 3H), 4.11 (s, 2H), 12.33 (s,
1H). Anal. Calcd for C9H10N4O3S3: C, 33.95; H, 3.17; N, 17.60; O, 15.08; S,
30.21. Found: C, 33.97; H, 3.19; N, 17.62; O, 15.07; S, 30.20.
1
3432, 2939, 1738, 1581, 1252, 1185, 1079; H NMR (DMSO-d6): δ 2.90 (t,
J ꢀ= ꢀ 7 Hz, 2H), 3.615 (s, 3H), 4.15 (s, 2H), 4.42 (t, J ꢀ= ꢀ 7 Hz, 2H), 12.43 (s, 1H).
Anal. Calcd for C9H10N4O3S3: C, 33.95; H, 3.17; N, 17.60; O, 15.08; S, 30.21.
Found: C, 33.94; H, 3.16; N, 17.64; O, 15.05; S, 30.23.
Butylꢀ3-[(5-((4-oxothiazolidin-2-ylidene)amino)-1,3,4-thiadia-
zol-2-yl)thio]propanoate (8c)ꢀYield 72%; mp 111–112°C, IR (cm-1):
1
Butyl 3-[5-((4-oxothiazolidin-2-ylidene)amino)-2-thioxo-1,3,4-thia-
diazol-3(2H)-yl]propanoate (6c)ꢀYield 61%; mp 154–155°C, IR (cm-1):
3432, 2960, 1726, 1634, 1575, 1244, 1181, 1082; 1H NMR (DMSO-d6): δ 0.86
(t, J ꢀ= ꢀ 7 Hz, 3H), 1.28 (m, J ꢀ= ꢀ 7 Hz, 2H), 1.54 (m, J ꢀ= ꢀ 7 Hz, 2H), 2.90 (t, J ꢀ= ꢀ 7
Hz, 2H), 4.02 (t, J ꢀ= ꢀ 7 Hz, 2H), 4.15 (s, 2H), 4.42 (t, J ꢀ= ꢀ 7 Hz, 2H), 12.44 (s,
1H). Anal. Calcd for C12H16N4O3S3: C, 39.98; H, 4.47; N, 15.54; O, 13.32; S,
26.69. Found: C, 39.99; H, 4.45; N, 15.53; O, 13.34; S, 26.68.
3405, 2958, 1732, 1594, 1171, 1248, 1056; H NMR (DMSO-d6): δ 0.88
(t, J ꢀ= ꢀ 8 Hz, 3H), 1.33 (m, J ꢀ= ꢀ8 Hz, H), 1.55 (m, J ꢀ= ꢀ 8 Hz, 2H), 2.84
(t, J ꢀ= ꢀ 8 Hz, 2H), 3.45 (t, J ꢀ= ꢀ 8 Hz, 2H), 4.05 (t, J ꢀ= ꢀ 8 Hz, 2H), 4.11 (s,
2H), 12.33 (s, 1H). Anal. Calcd for C12H16N4O3S3: C, 39.98; H, 4.47; N,
15.54; O, 13.32; S, 26.69. Found: C, 40.00; H, 4.46; N, 15.57; O, 13.30;
S, 26.70.
3-[(5-((4-Oxothiazolidin-2-ylidene)amino)-1,3,4-thiadiazol-2-yl)
thio]propanenitrile (8a)ꢀYield 63%; mp 208–210°C, IR (cm-1): 3432,
Received November 3, 2013; accepted November 19, 2013
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