Green synthesis of novel 2-pyrazolyl-1,3-thiazolidine-4-ones using 2-oxoimidazolidine-1,3-disulfonic acid

Article abstract of DOI:10.1515/hc-2017-0124

2-Oxoimidazolidine-1,3-disulfonic acid (OImDSA) is a recoverable catalyst for the synthesis of 1,3-thiazolidine-4-ones at room temperature in a one-pot procedure without using any organic solvents. Moreover, the catalyst can be easily recovered and recycled for five runs without significant loss of catalytic activity. The structures of the synthesized 1,3-thiazolidine-4-one compounds were confirmed by ¹H NMR, ¹³C NMR and FTIR spectral data and elemental analysis.

Full text of DOI:10.1515/hc-2017-0124

Heterocycl. Commun. 2017; aop
MGorheamemnadsNiykpnastshaned*s, LiesilaoZafrenFeokrvi aenld H2a-stpi Tyahrearkzhoorslayndl-1,3-
thiazolidine-4-ones using 2-oxoimidazolidine-1,3-
disulfonic acid
https://doi.org/10.1515/hc-2017-0124
employed for the synthesis of 1,3-thiazolidine-4-ones. To
the best of our knowledge, there is no report in the litera-
ture on the use of 2-oxoimidazolidine-1,3-disulfonic acid
(OImDSA) as a catalyst for the green synthesis of pyra-
zolyl-1,3-thiazolidine-4-ones. In the search for eco-friendly
alternatives to classical synthesis [10–22] and in continua-
tion of our studies to synthesize heterocyclic and pharma-
ceutical compounds under mild and practical protocols
[23–27], we report herein the synthesis of some novel pyra-
zolyl-1,3-thiazolidine-4-ones using OImDSA (Scheme 1).
Received June 11, 2017; accepted July 27, 2017
Abstract:
2-Oxoimidazolidine-1,3-disulfonic
acid
(OImDSA) is a recoverable catalyst for the synthesis of
1,3-thiazolidine-4-ones at room temperature in a one-pot
procedure without using any organic solvents. Moreover,
the catalyst can be easily recovered and recycled for five
runs without significant loss of catalytic activity. The
structures of the synthesized 1,3-thiazolidine-4-one com-
1
pounds were confirmed by H NMR, 13C NMR and FTIR
spectral data and elemental analysis.
Keywords: one-pot reaction; solid acid; 1,3-thiazolidine-
4-one; thioglycolic acid.
Results and discussion
Pyrazolecarbaldehyde 1a, 4-methoxyaniline 2a and thiogly-
colic acid 3 were mixed with 10 mL of H2O in the presence
of a catalytic amount of HCl and various solid catalysts,
namely montmorillonite K10, ZnCl2, L-proline, nano-Fe3O4,
nano-SiO2 and OImDSA (Scheme 2) or under solvent-free
condition using 2 mL of an ionic liquid such as [BMIM]
Br, [BMIM]OH and [BMIM]SOH. In these experiments,
OImDSA was the most efficient catalyst, not only in terms
of high yield of pyrazolyl-1,3-thiazolidine-4-one 4a but also
high reaction rate (92% yield in 1 h). Moreover, our results
showed that 0.1 g of OImDSA per 1 mmol of aldehyde 1a is
enough for the synthesis of 4a. The optimal temperature
for the synthesis of 4a is room temperature. Increasing the
temperature has no effect on the reaction time and yield.
Various pyrazolecarbaldehydes and anilines can
be utilized in this protocol. It has been shown that alde-
hydes with electron-withdrawing groups react faster than
the aldehydes with electron-releasing groups. The yields
obtained with substrates having electron-withdrawing
groups are also greater. To evaluate the reusability of the
OImDSA, the catalyst was separated from the reaction
medium by treatment with water. The aqueous solution
Introduction
Thiazolidine compounds contribute to various pharma-
cological effects. Thiazolidines are used as anti-seizure,
fungicidal, anti-bacterial, anti-tubercular, anti-inflam-
matory, anti-amoebic, anti-diabetic and local anesthetic
agents [1, 2]. Some of these compounds have also shown
anti-Parkinsonism [3], anti-oxidant [4], anti-convulsant
[5], anti-cancer [6], hypoglycemic [7] and non-narcotic
analgesic [8] activities. On the other hand, pyrazoles have
shown anti-bacterial, anti-tumor, anti-viral, anti-fungal,
anti-tubercular, anti-parasitic, anesthetic, anti-diabetic,
anti-inflammatory, analgesic and insecticidal activities [9].
In recent years, silica gel [10], SiCl4 [11], Bi(SCH2COOH)3
[12], ZnCl2 [13], N,N,N′,N′-Tetramethyl-O-(1H-benzotriazol-
1-yl)uronium hexafluorophosphate (HBTU) [14], [bmim]
[PF6] [15], Saccharomyces cerevisiae [16], 1,3-dicyclohexyl-
carbodiimide (DCC) [17], supported protic acid [18] and
nano-Fe3O4@SiO2 supported ionic liquid [19] have been
*Corresponding author: Mohammad Nikpassand, Department
of Chemistry, Rasht Branch, Islamic Azad University, Rasht, Iran,
e-mail: Nikpassand@iaurasht.ac.ir
Leila Zare Fekri: Department of Chemistry, Payame Noor University,
PO Box 19395-3697, Tehran, Iran
O
O
ClSO3H
HO3S
SO3H
HN
NH
N
N
Hasti Taherkhorsand: Department of Chemistry, Rasht Branch,
Islamic Azad University, Rasht, Iran
Scheme 1ꢀPreparation of 2-oxoimidazolidine-1,3-disulfonic acid
(OImDSA).
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ꢀM. Nikpassand et al.: Green synthesis of novel 2-pyrazolyl-1,3-thiazolidine-4-ones
R1
R1
O
S
NH2
N
CHO
O
OImDSA
rt
HS
OH
N
N
R2
N
N
R2
1a–d
2a–d
3
4a–k
4a: R1 = 4-Cl; R2 = 4-OMe
4b: R1 = H; R2 = 4-OMe
4i: R1 = 3-NO2; R2 = 4-NO2
4j: R1 = H; R2 = 4-Me
4e: R1 = 3-NO2; R2 = 2-Me-4-NO2
4f: R1 = H; R2 = H
4c: R1 = H; R2 = 2-Me-4-NO2
4d: R1 = 4-Cl; R2 = 2-Me-4-NO2
4k: R1 = 4-OH; R2= 4-NO2
4g: R1 = H; R2 = 4-NO2
4h: R1 = 4-Cl; R2 = 4-NO2
Scheme 2ꢀSynthesis of compounds 4a–k.
then filtered. The solid residue was washed with n-hexane (20 mL)
and dried under reduced pressure to give OImDSA as a white solid:
mp >300°C; IR: 984 (S=O symmetric stretch), 1315 (S=O asymmetric
stretch), 1661 (C=O stretch), 2963 (C-H aliphatic stretch), 3309 cm−1
was fractionally distilled under reduced pressure and the
recovered catalyst was reused in subsequent reactions.
After five successive runs, OImDSA showed virtually no
loss in efficiency regarding reaction time and yield.
1
(O-H stretch); H NMR δ: 3.63 (s, 4H, N-CH2-CH2-N), 13.35 (s, br., 2H,
-SO3H); 13C NMR: 51.4 (N-CH2-CH2-N), 152.5 (C=O). Anal. Calcd for
C3H6N2O7S2: C, 14.63; H, 2.46; N, 11.38. Found: C, 14.63; H, 2.47; N, 11.37.
Conclusions
An efficient protocol for the synthesis of compounds 4a–k
using OImDSA as an effective catalyst was developed. To
the best of our knowledge, this is the first report on the
synthesis of 1,3-thiazolidine-4-ones bearing pyrazole (0.1 g) was stirred at room temperature for 1–2 h. The progress of the
moiety in aqueous media.
General procedure for preparation of 4a–k
A mixture of a pyrazolecarbaldehyde 1 (1 mmol), an aniline 2
(1 mmol), thioglycolic acid 3 (1 mmol), H2O (10 mL) and OImDSA
reaction was monitored by TLC (EtOAc/petroleum ether, 1:2). After
completion of the reaction, the product was extracted with CHCl3 and
the aqueous phase containing catalyst OImDSA was fractionally dis-
tilled under reduced pressure. Then, the solution in CHCl3 was con-
centrated under reduced pressure and the residue was purified by
Experimental
column chromatography (EtOAc/petroleum ether, 1:2). The product
was crystallized from EtOH.
All commercial chemicals were used as received. Melting points
were measured on an Electro-thermal 9100 apparatus and are uncor-
2-(3-(4-Chlorophenyl)-1-phenyl-1H-pyrazol-4-yl)-3-(4-meth-
1
rected. H nuclear magnetic resonance (NMR) (500 MHz) and 13C
oxyphenyl)thiazolidin-4-one (4a)ꢀReaction time 60 min; yield
NMR (125 MHz) spectra were obtained on a Bruker DRX 500 Avance
92%; yellow solid, mp 242–244°C; IR: 1502, 1541, 1600 (C=C aromatic
spectrometer using CDCl3 as solvent and TMS as the internal stand-
stretch), 1731 (C=O stretch), 2981 (C-H aliphatic stretch), 3126 cm−1
ard. Fourier transform infrared (FT-IR) spectra were recorded as KBr
(C-H aromatic stretch); 1H NMR: δ 3.28 (d, Jꢁ=ꢁ15.3 Hz, 1H, CH2-S), 3.50
pellets on a Shimadzu FT-IR-8400S spectrometer. Elemental analyses
(d, Jꢁ=ꢁ15.3 Hz, 1H, CH2-S), 3.52 (s, 3H, CH3O), 5.48 (s, 1H, N-CH-S), 7.32
were done on a Carlo-Erba EA1110CNNO-S analyzer.
(t, Jꢁ=ꢁ7.4 Hz, 1H, Ar), 7.43–7.49 (m, 4H, Ar), 7.73–7.80 (m, 4H, Ar), 8.22
(s, 1H, N-CH=C); 13C NMR: δ 32.9, 40.4, 60.5, 118.0, 125.5, 127.4, 127.8,
128.4, 128.7, 129.5, 129.8, 133.6, 138.8, 143.1, 168.3 (C=O). Anal. Calcd
Synthesis of 2-oxoimidazolidine-1,3-disulfonic acid
(OImDSA)
for C25H20ClN3O2S: C, 65.00; H, 4.36; N, 9.10. Found: C, 65.02; H, 4.35;
N, 9.08.
A flask (500 mL) with imidazolidin-2-one (8.6 g, 0.1 mol) was equipped 2-(3-(4-Chlorophenyl)-1-phenyl-1H-pyrazol-4-yl)-3-(4-methoxy-
with a constant pressure dropping funnel containing chlorosulfonic phenyl)thiazolidin-4-one (4b)ꢀReaction time 70 min, yield 90%;
acid (23.3 g, 0.2 mol) and a gas outlet tube which was dipped into yellow solid; mp 231–233°C; IR: 1288 (C-O aromatic stretch), 1500,
water to dissolve the generated HCl gas during the reaction. The flask 1541, 1596 (C=C aromatic stretch), 1737 (C=O stretch), 2977 (C-H ali-
1
was placed into an ice bath and chlorosulfonic acid was added drop- phatic stretch), 3058 cm−1 (C-H aromatic stretch); H NMR: δ 3.29
wise over a period of 20 min and the resulting mixture was stirred for (d, Jꢁ=ꢁ15.2 Hz, 1H, CH2-S), 3.49 (d, Jꢁ=ꢁ15.2 Hz, 1H, CH2-S), 3.58 (s, 3H,
an additional 20 min. The temperature of the mixture was brought CH3O), 5.49 (s, 1H, N-CH-S), 7.30 (td, Jꢁ=ꢁ7.9, 0.7 Hz, 2H, CH=C- OCH3),
up to the room temperature and stirring was continued for an addi- 7.37–7.41 (m, 2H, Ar), 7.45–7.48 (m, 6H, Ar), 7.76 (dd, Jꢁ=ꢁ8.4 Hz and
tional 60 min. The mixture was triturated with n-hexane (20 mL) and 0.6 Hz, 2H, Ar), 7.80 (d, Jꢁ=ꢁ8.4 Hz, 2H, CH=C-Cl), 8.09 (s, 1H, N-CH=C);
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13C NMR δ: 32.9, 43.5, 60.5, 118.0, 125.7, 127.1, 127.3, 127.4, 127.5, 127.6, (d, Jꢁ=ꢁ15.2 Hz, 1H, CH2-S), 5.50 (s, 1H, N-CH-S), 7.28–7.32 (m, 2H, Ar),
128.4, 131.3, 138.6, 150.0, 168.8 (C=O). Anal. Calcd for C25H21N3O2S: C, 7.39–7.42 (m, 2H, Ar), 7.44–7.49 (m, 6H, Ar), 7.76 (d, Jꢁ=ꢁ7.9 Hz, 2H, CH-
70.24; H, 4.95; N, 9.83. Found: C, 70.26; H, 4.97; N, 9.81.
CH=C-NO2), 7.82 (dd, Jꢁ=ꢁ8.5 Hz and 1.4 Hz, 2H, CH=C-NO2), 8.23 (s,
1H, N-CH=C); 13C NMR δ: 32.9, 43.4, 117.3, 117.9, 118.0, 125.6, 126.7, 127.1,
2-(1,3-Diphenyl-1H-pyrazol-4-yl)-3-(2-methyl-4-nitrophenyl) 127.2, 127.4, 127.5, 127.6, 127.7, 128.4, 131.2, 138.6, 150.0, 168.7 (C=O).
thiazolidin-4-one (4c)ꢀReaction time 75 min; yield 86% of yellow Anal. Calcd for C24H18N4O3S: C, 65.14; H, 4.10; N, 12.66. Found: C, 65.12;
solid; mp 237–239°C; IR: 1363, 1541 (NO2 stretch), 1450, 1500, 1596 (C=C H, 4.09; N, 12.63.
aromatic stretch), 1730 (C=O stretch), 2981 (C-H aliphatic stretch),
1
3126 cm−1 (C-H aromatic stretch); H NMR: δ 3.30 (d, Jꢁ=ꢁ15.2 Hz, 1H, 2-(3-(4-Chlorophenyl)-1-phenyl-1H-pyrazol-4-yl)-3-(4-nitrophenyl)
CH2-S), 3.50 (d, Jꢁ=ꢁ15.2 Hz, 1H, CH2-S), 3.58 (s, 3H, CH3), 5.50 (s, 1H, thiazolidin-4-one (4h)ꢀReaction time 80 min; yield 79% of yellow
N-CH-S), 7.31 (t, Jꢁ=ꢁ7.4 Hz, 1H, Ar), 7.40–7.42 (m, 1H, Ar), 7.45–7.49 solid, mp 239–241°C; IR: 1380 (NO2 symmetric stretch), 1544 (NO2 asym-
(m, 7H, Ar), 7.75–7.78 (m, 2H, Ar), 7.80–7.82 (m, 2H, Ar), 8.23 (s, 1H, metric stretch), 1731 (C=O stretch), 2981 cm−1 (C-H aliphatic stretch);
N-CH=C); 13C NMR: δ 30.9, 40.4, 43.5, 60.5, 60.6, 118.0, 125.7, 127.1, 127.3, 1H NMR: δ 3.31 (d, Jꢁ=ꢁ15.2 Hz, 1H, CH2-S), 3.53 (d, Jꢁ=ꢁ15.2 Hz, 1H, CH2-S),
127.4, 127.5, 127.6, 128.4, 131.3, 138.6, 150.0, 168.8 (C=O). Anal. Calcd 5.51 (s, 1H, N-CH-S), 7.36–7.37 (m, 1H, Ar), 7.46–7.50 (m, 5H, Ar), 7.52 (dd,
for C25H20N4O3S: C, 65.77; H, 4.42; N, 12.27. Found: C, 65.75; H, 4.39; Jꢁ=ꢁ5.6 Hz and 3.2 Hz, 1H, Ar), 7.75–7.85 (m, 6H, Ar), 8.26 (s, 1H, N-CH=C);
N, 12.29.
13C NMR δ: 32.7, 44.0, 114.8, 118.2, 119.7, 123.9, 125.8, 128.4, 129.4, 129.8,
138.7, 150.3, 151.3, 170.3 (C=O). Anal. Calcd for C24H17ClN4O3S: C, 60.44; H,
2-(3-(4-Chlorophenyl)-1-phenyl-1H-pyrazol-4-yl)-3-(2-methyl- 3.59; N, 11.75. Found: C, 60.45; H, 3.61; N, 11.72.
4-nitrophenyl)thiazolidin-4-one (4d)ꢀReaction time 60 min;
yield 87% of yellow solid; mp 240–242°C; IR: 1400, 1539 (NO2 stretch), 3-(4-Nitrophenyl)-2-(3-(3-nitrophenyl)-1-phenyl-1H-pyrazol-
1454, 1500, 1598 (C=C aromatic stretch), 1731 (C=O stretch), 2981 (C-H 4-yl)thiazolidin-4-one (4i)ꢀReaction time 90 min; yield 84% of
aliphatic stretch), 3128 cm−1 (C-H aromatic stretch); 1H NMR: δ 3.24 (d, yellow solid, mp 263–265°C: IR: 1350 (NO2 symmetric stretch), 1533
Jꢁ=ꢁ15.2 Hz, 1H, CH2-S), 3.49 (d, Jꢁ=ꢁ15.2 Hz, 1H, CH2-S), 3.55 (s, 1H, CH3), (NO2 asymmetric stretch), 1598, 1627 (C=C aromatic stretch), 1731
1
5.45 (s, 1H, N-CH-S),7.26–7.30 (m, 2H, Ar),7.40–7.45 (m, 6H, Ar), 7.71–7.73 (C=O stretch), 2923 cm−1 (C-H aliphatic stretch); H NMR: δ 3.30 (d,
(m, 2H, Ar), 7.75–7.78 (m, 2H, CH=C-Cl), 8.20 (s, 1H, N-CH=C); 13C NMR: Jꢁ=ꢁ15.3 Hz, 1H, CH2-S), 3.53 (d, Jꢁ=ꢁ15.3 Hz, 1H, CH2-S), 5.54 (s, 1H, N-CH-
δ 32.7, 40.3, 43.2, 60.4, 60.5, 117.8, 117.9, 125.7, 127.3, 127.6, 128.3, 128.6, S), 7.35 (t, Jꢁ=ꢁ7.4 Hz, 2H, Ar), 7.48–7.52 (m, 3H, Ar), 7.67 (t, Jꢁ=ꢁ8.0 Hz, 2H,
129.7, 133.1, 138.4, 148.7, 168.1 (C=O). Anal. Calcd for C25H19ClN4O3S, %: Ar), 7.76–7.80 (m, 3H, Ar), 8.24–8.76 (m, 4H, Ar); 13C NMR: δ 43.3, 60.6,
C, 61.16; H, 3.90; N, 11.41. Found: C, 61.14; H, 3.87; N, 11.39.
118.1, 121.9, 122.4, 126.2, 127.8, 128.5, 128.6, 133.4, 168.7 (C=O). Anal.
Calcd for C24H17N5O5S: C, 59.13; H, 3.51; N, 14.37. Found: C, 59.15; H,
3-(2-Methyl-4-nitrophenyl)-2-(3-(3-nitrophenyl)-1-phenyl-1H- 3.49; N, 14.39.
pyrazol-4-yl)thiazolidin-4-one (4e)ꢀReaction time 70 min; yield
91% of yellow solid; mp 251–253°C; IR: 1353, 1533 (NO2 stretch) 2-(1,3-Diphenyl-1H-pyrazol-4-yl)-3-p-tolylthiazolidin-4-one
1456, 1595 (C=C aromatic stretch), 1731 (C=O stretch), 2981 (C-H ali- (4j)ꢀReaction time 90 min; yield 84% of yellow solid; mp 246–248°C;
1
phatic stretch), 3128 cm−1 (C-H aromatic stretch); H NMR: δ 3.28 (d, IR: 1350 (NO2 symmetric stretch), 1533 (NO2 asymmetric stretch),
Jꢁ=ꢁ15.1 Hz, 1H, CH2-S), 3.34 (d, Jꢁ=ꢁ15.1 Hz, 1H, CH2-S), 3.56 (s, 3H, CH3), 1598, 1627 (C=C aromatic stretch), 1731 (C=O stretch), 2923 cm−1 (C-H
1
5.52 (s, 1H, N-CH-S), 7.31–7.35 (m, 1H, Ar), 7.45–7.48 (m, 3H, Ar), 7.64– aliphatic stretch); H NMR δ: 3.32 (d, Jꢁ=ꢁ15.2 Hz, 1H, CH2-S), 3.54 (d,
7.66 (m, 1H, Ar), 7.66–7.76 (m, 3H, Ar), 8.21 (d, Jꢁ=ꢁ2.0 Hz, 1H, Ar), 8.23 Jꢁ=ꢁ15.2 Hz, 1H, CH2-S), 3.63 (s, 3H, CH3), 5.54 (s, 1H, N-CH-S), 7.34 (t,
(d, Jꢁ=ꢁ2.0 Hz, 1H, CH3-CH-CH=C-NO2), 8.25 (s, 1H, N-CH=C), 8.72 (t, Jꢁ=ꢁ7.6 Hz, 1H, Ar), 7.63 (t, Jꢁ=ꢁ7.6 Hz, 1H, Ar), 7.48–7.55 (m, 6H, Ar), 7.80
Jꢁ=ꢁ1.8 Hz, 1H, Pyrazolyl-CH=C-NO2); 13C NMR δ: 32.8, 40.3, 60.4, 118.0, (d, Jꢁ=ꢁ7.6 Hz, 2H, Ar), 7.85 (dd, Jꢁ=ꢁ7.6 Hz and 1.2 Hz, 2H, Ar), 8.27 (s, 1H,
118.3, 121.8, 122.3, 126.1, 127.7, 128.4, 128.5, 128.6, 133.1, 133.3, 138.3, N-CH=C); 13C NMR: δ 34.0, 41.48, 44.6, 119.0, 126.7, 128.2, 128.3, 128.5,
147.3, 147.4, 168.2 (C=O). Anal. Calcd for C25H19N5O5S: C, 59.87; H, 3.82; 128.6, 129.0, 129.5, 129.7, 132.4, 139.7, 151.1, 169.8 (C=O). Anal. Calcd for
N, 13.96. Found: C, 59.85; H, 3.84; N, 13.95.
C25H21N3OS: C, 72.97; H, 5.14; N, 10.21. Found: C, 72.95; H, 5.15; N, 10.19.
2-(1,3-Diphenyl-1H-pyrazol-4-yl)-3-phenylthiazolidin-4-one 2-(3-(4-Hydroxyphenyl)-1-phenyl-1H-pyrazol-4-yl)-3-(4-nitro-
(4f)ꢀReaction time 60 min; yield 89% of yellow solid; mp 221–223°C, phenyl)thiazolidin-4-one (4k)ꢀReaction time 75 min, 87% of
IR: 1498, 1539, 1596 (C=C aromatic stretch), 1733 (C=O stretch), 2981 yellow solid, mp 254–256°C; IR: 1276 (C-O aromatic), 1502 (NO2 sym-
1
(C-H aliphatic stretch), 3058 cm−1 (C-H aromatic stretch); H NMR: δ metric stretch), 1533 (NO2 asymmetric stretch), 1602 (C=C aromatic
3.29 (d, Jꢁ=ꢁ15.1 Hz, 1H, CH2-S), 3.52 (d, Jꢁ=ꢁ15.1 Hz, 1H, CH2-S), 5.53 (s, stretch), 1726 (C=O stretch), 2923 (C-H aliphatic stretch), 3425 cm−1
1
1H, N-CH-S), 7.18–7.30 (m, 2H, Ar), 7.40–7.44 (m, 2H, Ar) 7.46–7.52 (m, (O-H aliphatic stretch); H NMR: δ 3.32 (d, Jꢁ=ꢁ15.3 Hz, 1H, CH2-S),
2H, Ar), 7.77 (d, Jꢁ=ꢁ8.2, 2.4 Hz, 2H, Ar), 7.83 (dd, Jꢁ=ꢁ8.2 Hz and 2.4 Hz, 3.54 (d, Jꢁ=ꢁ15.3 Hz, 1H, CH2-S), 5.48 (s, 1H, N-CH-S), 6.91 (d, Jꢁ=ꢁ8.4 Hz,
2H, Ar), 8.26 (s, 1H, N-CH=C); 13C NMR: δ 43.5, 44.5, 119.0, 119.1, 126.7, 2H, CH=C-OH), 7.29–7.35 (m, 2H, Ar), 7.49–7.51 (m, 4H, Ar), 7.68 (d,
128.2, 128.3, 128.4, 128.6, 129.4, 132.4, 139.7, 151.1, 169.8 (C=O). Anal. Jꢁ=ꢁ8.2 Hz, 2H, Ar), 7.75–7.78 (m, 3H, Ar), 8.22 (s, 1H, N-CH=C); 13C NMR:
Calcd for C24H19N3OS: C, 72.52; H, 4.82; N, 10.57. Found: C, 72.50; H, δ 33.9, 44.6, 115.6, 118.7, 119.1, 124.4, 126.7, 128.1, 129.5, 129.9, 139.6, 151.1,
4.79; N, 10.59.
156.3, 170.0 (C=O). Anal. Calcd for C24H18N4O4S: C, 62.87; H, 3.96; N,
12.22. Found: C, 62.86; H, 3.97; N, 12.20.
2-(1,3-Diphenyl-1H-pyrazol-4-yl)-3-(4-nitrophenyl)thiazolidin-
4-one (4g)ꢀReaction time 75 min; yield 83% of yellow solid; mp
224–226°C; IR 1361 (NO2 symmetric stretch), 1542 (NO2 asymmetric
stretch), 1730 (C=O stretch), 2981 (C-H aliphatic stretch), 3060 cm−1
(C-H aromatic stretch); 1H NMR: δ 3.29 (d, Jꢁ=ꢁ15.2 Hz, 1H, CH2-S), 3.50
Acknowledgments: We gratefully acknowledge the
financial support from the Islamic Azad University, Rasht
Branch, Iran.
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