Synthesis of 5-Alkylidene-2,4-thiazolidinediones and Rhodanines Promoted by Propylamino-functionalized Nano-structured SBA-15

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Organic Preparations and Procedures
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Synthesis of 5-Alkylidene-2,4-
thiazolidinediones and Rhodanines
Promoted by Propylamino-functionalized
Nano-structured SBA-15
a
a
b
Hojat Veisi , Alireza Naeimi , Behrooz Maleki , Samaneh Sedigh
b
c
Ashrafi & Alireza Sedrpoushan
a
Department of Chemistry, Payame Noor University (PNU),
9395-4697 Tehran, Iran
Click for updates
1
b
Department of Chemistry, Hakim Sabzevari University, Sabzevar,
Khorasan, Iran
c
Institute of Industrial Chemistry, Iranian Research Organization for
Science and Technology, Tehran, Iran
Published online: 26 Jun 2015.
To cite this article: Hojat Veisi, Alireza Naeimi, Behrooz Maleki, Samaneh Sedigh Ashrafi & Alireza
Sedrpoushan (2015) Synthesis of 5-Alkylidene-2,4-thiazolidinediones and Rhodanines Promoted
by Propylamino-functionalized Nano-structured SBA-15, Organic Preparations and Procedures
International: The New Journal for Organic Synthesis, 47:4, 1-7, DOI: 10.1080/00304948.2015.1052321
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Organic Preparations and Procedures International, 47:1–7, 2015
Copyright Ó Taylor & Francis Group, LLC
ISSN: 0030-4948 print / 1945-5453 online
DOI: 10.1080/00304948.2015.1052321
Synthesis of 5-Alkylidene-2,4-thiazolidinediones
and Rhodanines Promoted by Propylamino-
functionalized Nano-structured SBA-15
1
Hojat Veisi, Alireza Naeimi, Behrooz Maleki, Samaneh Sedigh
1
2
2
Ashrafi, AND Alireza Sedrpoushan
3
1
Department of Chemistry, Payame Noor University (PNU), 19395-4697
Tehran, Iran
2
Department of Chemistry, Hakim Sabzevari University, Sabzevar,
Khorasan, Iran
3
Institute of Industrial Chemistry, Iranian Research Organization for Science
and Technology, Tehran, Iran
Molecules containing the 2,4-thiazolidinedione and rhodanine rings show a wide range of
pharmacological activities including anti-microbial, anti-convulsant, anti-bacterial, anti-
viral, anti-diabetic and anti-convulsant effects. Furthermore, rhodanine-based compounds
are useful as small molecular inhibitors of numerous targets such as HCV NS3 protease,
aldose reductase, b-lactamase, UDP-N-acetyl-muramate/L-alanine ligase, anti-diabetic
1
agents, cathepsin D, and histidinede-carboxylase.
Rhodanines have been synthesized by various methods such as by addition of isothio-
cyanates to mercaptoacetic acid followed by acid-catalyzed cyclization, and by the reac-
tion of ammonia or primary amines with carbon disulfide and chloroacetic acid in the
2
,3
presence of bases. The condensation of aromatic aldehydes or ketones at the nucleo-
philic C-5 active methylene of rhodanines has been performed using tetra(n-butyl)ammo-
4
nium hydroxide, under microwave in the presence of tetra(n-butyl)ammonium bromide,
5
6
-(n-butyl)-3-methyl-imidazolium hydroxide, sodium acetate under microwave in gla-
1
cial acetic acid, refluxing in toluene (NH OAc for ketones), 2-hydroxyethylammonium
7
8
4
9
formate, piperidine in EtOH, acetic anhydride, alum (KAl(SO ) .12H O), polyeth-
1
ylene glycol (PEG), electrolysis/EtOH/NaBr, and silica based substituted pyridine.
10
11
12
4
2
2
3
14
15
However, the reported methods suffer from some drawbacks such as prolonged reaction
times, the use of environmentally unfavorable solvents and low yields. The present work
describes the use of SBA-15-PrNH (Fig. 1) as a solid base catalyst for the preparation of
2
rhodanines and 5-alkylidene-2,4-thiazolidinediones.
Received July 10, 2014; in final form February 8, 2015.
Address correspondence to Hojat Veisi, Department of Chemistry, Payame Noor
University (PNU), 19395-4697 Tehran, Iran, E-mail: hojatveisi@yahoo.com; or Behrooz Maleki,
Department of Chemistry, Hakim Sabzevari University, Sabzevar, Khorasan, Iran. E-mail:
malekibehrooz@gmail.com
Color versions of one or more of the figures in this article can be found online at www.
tandfonline.com/uopp
1

2
Maleki et al.
Figure 1 Nano SBA-15-PrNH2.
This catalyst has several advantages over homogeneous organic basis catalysts,
1
6–21
namely easy recovery and recyclability and simple product isolation.
We first
decided to examine the Knoevenagel condensation of aromatic aldehydes bearing various
substituents such as hydroxy, chloro, nitro, methoxy groups with the C-5 methylene of
rhodanine in the presence of basic nano SBA-15-PrNH in ethanol. The reaction pro-
2
ꢀ
ceeded smoothly and in high yields at 50 C for 2 hours (Scheme 1, Table 1).
The catalyst plays a crucial role in the success of the reaction in terms of the rate and
the yields. For example, the reaction of benzaldehyde with rhodanine carried out in the
ꢀ
absence of the catalyst by stirring at 50 C for 12 hours gave the product in only 20%
yield. The use of other solid basic catalysts such as aminomethylated polystyrene and
poly(4-vinylpyridine) led to 65%, and 60% yields respectively, suggesting that nano
SBA-15-PrNH is the better basic catalyst for this reaction. This prompted us to study the
2
activity of the recycled catalyst. After separation of products, the catalyst was re-used
Scheme 1

5-Alkylidene-2,4-thiazolidinediones and Rhodanines
3
Table 1
Synthesis of Rhodanine, 2,4-Thiazolidinedione and 2-Amino-5-alkylidenethiazol-4-one
Derivatives
ꢀ
mp ( C)
Compounds
Time (h)
Yield (%)
Found
Lit.
4
4
4
4
4
4
4
3
3
3
3
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
a
b
c
d
e
f
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
90
90
95
85
95
95
88
95
92
92
90
95
90
90
85
95
90
80
90
92
75
85
202–204
250–253
261–263
184–185
230–232
225–227
271–272
240–241
234–235
178–179
281–281
213–214
265–266
280–281
192–195
178–179
228–230
212–214
141–143
171–173
160–162
172–175
199–202
250–252
263–264
185–186
231–232
224–230
273–274
g
h
i
4
240
235
4
4
j
180
281
4
k
l
4
215
270
4
m
n
a
b
c
d
e
f
4
281
1
1
1
1
1
1
1
1
5
5
5
5
5
5
5
5
192–194
178–180
228–230
214–216
140–142
172–174
158–160
172–174
g
h
(without further purification) without significant decrease of the yields which ranged from
8
6–90%. Our preliminary attempts of the reaction of acetaldehyde (1 mmol) with 2,4-
thiazolidinedione (1 mmol) in the presence of SBA-15-PrNH (0.05 g) failed to yield the
2
corresponding product; instead a mixture of unidentifiable impurities was obtained.
The use of this catalyst allowed us to synthesize a variety of 2-amino-5-alkylidene-
thiazol-4-ones (4) from rhodanine, amines and a variety of ketones (Scheme 1). The
desired products (Table 1) were obtained in good to excellent yields. We next examined
a variety of amines bearing a wide range of functional groups to determine the scope and
generality of this reaction to give 2-amino-5-alkylidenethiazol-4-ones (Table 1). This
method was also utilized for the con-densation of various aldehydes with 2,4-thiazolidi-
ꢀ
nedione in ethanol at 50 C for 2 hours to prepare 3 in 90–95% yields (Scheme 1). The
conditions were compatible with the presence of various substituents such as nitro,
methyl, chloro, hydroxy, methoxy groups; no significant substituent effect was observed
on the reaction time or yield of products (Table 1).
The present article describes a convenient preparation of the amine-functionalized
SBA-15 via reaction of 3-aminopropyltriethoxysilane (APTES) with SBA-15 according
1
9–20
to the literature procedure.
The catalyst (SBA-15/pr-NH ) was characterized by scan-
2
ning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray dif-
fraction (XRD) and FTIR as well as elemental analysis.

4
Maleki et al.
The reusability and recycling of SBA-15-PrNH was ascertained as follows. A mix-
2
ture of benzaldehyde (1 mmol), 2,4-thiazolidinedione (1 mmol) and SBA-15-Pr-NH2
ꢀ
(0.05 g) in ethanol (5 mL) was heated at 50 C in an oil bath for 2 hours. When the reac-
tion was complete, the catalyst was filtered, washed with acetone, dried at 40 C for
ꢀ
5–6 hours and was re-used at least three times to give yields of 90%, 86%, and 81% for
3a after 2 hours. Furthermore, this catalyst was also re-used for the preparation of 3h and
4b in yields ranging from 95–84% and 95–88% respectively.
The amino group of the catalyst is the key factor and performs two functions, first via
formation an imine intermediate and second by abstraction of a proton from the ring. A
proposed mechanism for the reaction of 2,4-thiazolidinedione and rhodanines with car-
bonyl compounds catalyzed by SBA-15 (SBA-15-PrNH ) catalyst is illustrated in
2
Scheme 2. The carbonyl compound 1 condenses with the amino group to form the inter-
mediate of imine A and this is followed by abstraction of the a-proton of 2,4-thiazolidine-
dione (or of rhodanine 2) by another amino group and then by the nucleophilic attack of
the deprotonated 2,4-thiazolidinedione (or rhodanine) B on imine A, leading to product 3.
Similarly, it is probable that the amino group of SBA-15-PrNH similarly catalyzes the
2
condensation of the amines to the 2-amino-5-alkylidene compounds.
Table 2 shows a comparison of our results with those obtained using other proce-
dures for the synthesis of rhodanines, 2,4-thiazolidinedione and 2-amino-5-alkylidene-
thiazol-4-ones. The data illustrate the promising features of this method in terms of
reaction times and yields of the products compared with those previously reported.
Although the use of SBA-15-PrNH clearly shows that reaction times are not better than
2
some of the other methods in literature, the novelty and value of our results are principally
related to comparison with other amine basic catalysts such as aminomethylated polysty-
rene, poly(4-vinylpyridine), triethylamine, poly(amidoamine) (PAMAM) dendrimers
(G ), piperidine, morpholine, triethanolamine (TEA), diethanolamine (DEA) and diethyl-
amine; these catalysts lead to low yields in longer times when compared with SBA-15-
1
PrNH under the same reaction conditions.
2
In conclusion, the propylamine-functionalized SBA-15 material (SBA-15-PrNH2)
catalyst worked well in the Knoevenagel condensation of various aromatic aldehydes
with 2,4-thiazolidinedione and rhodanines with excellent selectivity and conversion
for the synthesis of the corresponding ylidene derivatives. We have also developed a
novel protocol using SBA-15-Pr-NH as silica-based heterogeneous catalyst for the
2
one-pot three-component condensation of rhodanine, amines, and ketones to yield 2-
amino-5-alkylidenethiazol-4-ones. This “heterogenized” catalyst combines the advan-
tages of both homo- and heterogeneous systems and therefore provides an easily
Scheme 2

5-Alkylidene-2,4-thiazolidinediones and Rhodanines
5
Table 2
Comparison of Different Conditions for the Synthesis of Rhodanines, 2,4-Thiazolidine-
diones and 2-Amino-5-alkylidenethiazol-4-ones
Time Yield
(min) (%)
Entry
Compounds
Conditions
3
f
Tetrabutylammonium hydroxide/H2O/
4
120
95
ꢀ
EtOH/50 C
Tetrabutylammonium bromide/H2O/MWI
5
8
30
75
95
1
-(n-Butyl)-3-methylimidazolium
6
hydroxide/H2O/rt
7
NaOAc/AcOH/MVI
Electrolysis/EtOH/NaBr
This work
10
40
81
85
95
1
4
120
3
4
b
b
Tetrabutylammonium hydroxide/H2O/
4
120
90
ꢀ
EtOH/50 C
Acetic anhydride/1100C
1
1
720
50
64
95
95
ꢀ
12
Alum/H2O/90 C
This work
120
Silica-based substituted pyridine/H2O/
15
68
91
95
ꢀ
EtOH/100 C
This work
120
recyclable and re-usable solid catalyst that has uniform and precisely engineered
active sites similar to those of its homogeneous counterpart. The major advantages
of the present method are much more rapid reactions, facile work-up procedures,
good to excellent yields, and avoidance of the use of hazardous and toxic organic
solvents and catalysts.
Experimental Section
1
IR spectra were obtained as KBr pellets on a Shimadzu 435-U-04 spectrophotometer. H
NMR spectra were acquired on a Bruker 300 MHz spectrometer in DMSO-d or CDCl
6
3
using TMS as an internal reference. Melting points were determined in open capillary
tubes on a Stuart BI Branstead Electrothermal Cat No:IA9200 apparatus and are
uncorrected.
Preparation of SBA-15
Four grams of pluronic P123 triblock polymer (EO PO EO , average molecular weight
2
0
70
20
of 5800, Aldrich) as the template was dissolved in 50 mL of water and the solution was

6
Maleki et al.
stirred for 5 hrs at room temperature. It was then added to 120 mL of a stirred solution of
M aqueous hydrochloric acid and stirred for 2h. Then, 8.5 g (40.mmol) of tetraethyl
orthosilicate as the siliceous source was added to that solution and the whole was stirred
2
ꢀ
ꢀ
for 24 hrs at 35 C. The mixture was then aged at 80 C for 24 hrs without stirring. After
that time, the solid product was collected, washed with deionized water (50 mL), and air-
dried overnight. The P123 was removed by thorough washing with hot ethanol/water
ꢀ
(
3:2) using a Soxhlet extractor for 24 hrs. The residue was dried overnight at 110 C in air
ꢀ
atmosphere. The solid was calcined at 550 C for 8 hrs in air atmosphere to completely
remove the surfactant template (pluronic P123 triblock polymer), and a white powder
1
6
(
SBA-15) was obtained.
Preparation of SBA-15-PrNH2
1
9,20
This is adapted from the published procedure.
ꢀ ꢀ
SBA-15 (5.0 g) calcined for 8 hrs at
50 C was activated by drying at 200 C under vacuum for 5 hrs followed by reflux with
5
stirring in dry toluene (150 ml) for 10 hrs to remove all traces of moisture. Then 3-amino-
propyltrimethoxysilane (7 ml, 30.2 mmol, Aldrich) was gradually added to the mixture
ꢀ
and the reaction was heated at 110 C for a further 24 hrs. The white solid formed was col-
ꢀ
lected, washed with dried toluene (20 ml) and then dried under vacuum at 70 C for 10 h.
0
The resulting material was identified as SBA-15-PrNH2.
2
General Procedure for the Preparation of Rhodanines (3a–3g) and 2,4-
Thiazolidinediones (3h–3n)
A mixture of the aromatic aldehyde (1 mmol), 2,4-thiazolidinedione (0.133, 1 mmol) [or
rhoda-nine (0.117 g, 1 mmol)] and SBA-15-Pr-NH (0.05 g) in EtOH (5 mL) was stirred
2
ꢀ
at 50 C in an oil bath for 2 hours; the progress of the reaction was monitored by TLC
(2:1 n-hexane/ethyl acetate). After completion of the reaction, 10 mL acetone was added
and the mixture was filtered to remove the catalyst. Upon addition of 5 mL H O to the fil-
trate, the precipitated solid obtained was collected and recrystallized from ethanol to give
2
1
the pure products, characterized by comparison of their H NMR spectra and melting
points with those reported in the literature.
General Procedure for the Preparation of 2-Amino-5-alkylidenethiazol-4-ones
(
4a–4h)
A mixture of rhodanine (0.117 g, 1 mmol), ketone (1 mmol), amine (1 mmol), and SBA-
5-Pr-NH (0.05 g) in aqueous ethanol (1:1, 4 mL) was stirred under reflux for 2 hours;
1
2
the progress of the reaction was monitored by TLC (2:1 n-hexane/ethyl acetate). After
completion of the reaction, 10 mL acetone was added and the mixture was filtered to
remove the catalyst. Addition of 5 mL H O to the filtrate gave a solid which was col-
2
lected and recrystallized from ethanol (80%) or purified by column chromatography to
afford the pure product. All the products are known and were characterized by compari-
1
son of their H NMR and melting point data with those reported in the literature.
Acknowledgments
We are thankful to Hakim Sabzevari (research council) and Payame Noor University
(PNU) partial supported of this work.

5-Alkylidene-2,4-thiazolidinediones and Rhodanines
7
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