Succinimidinium N-sulfonic acid hydrogen sulfate as an efficient ionic liquid catalyst for the synthesis of 5-arylmethylene-pyrimidine-2,4,6-trione and pyrano[2,3-d]pyrimidinone derivatives

Article abstract of DOI:10.1007/s11164-015-2289-6

Succinimidinium N-sulfonic acid hydrogen sulfate ([SuSA-H]HSO₄) as a new ionic liquid is prepared and characterized using a variety of techniques, including infrared spectra (FT-IR), ¹H and ¹³C NMR, scanning electron microscopy, a mass spectra method, as well as by Hammett acidity function. The prepared reagent is efficiently able to catalyze the preparation of 5-arylmethylene-pyrimidine-2,4,6-triones via the condensation of aldehydes and barbituric acid. Further studies showed that the condensation of aldehydes with barbituric acid and malononitrile leading to pyrano[2,3-d]pyrimidinone derivatives can also be efficiently promoted in the presence of this reagent. The present methodology offers several advantages, including ease of the preparation and handling of the catalyst, simple and easy work-up, short reaction times, high yields of the products and recyclability of the catalyst.

Full text of DOI:10.1007/s11164-015-2289-6

Res Chem Intermed
DOI 10.1007/s11164-015-2289-6
Succinimidinium N-sulfonic acid hydrogen sulfate
as an efficient ionic liquid catalyst for the synthesis
of 5-arylmethylene-pyrimidine-2,4,6-trione
and pyrano[2,3-d]pyrimidinone derivatives
Masoumeh Abedini1 Farhad Shirini1
•
•
Javad Mohammad-Alinejad Omran1
Mohadeseh Seddighi1 Omid Goli-Jolodar1
•
•
Received: 15 August 2015 / Accepted: 21 September 2015
Ó Springer Science+Business Media Dordrecht 2015
Abstract Succinimidinium N-sulfonic acid hydrogen sulfate ([SuSA-H]HSO4) as a
new ionic liquid is prepared and characterized using a variety of techniques, including
1
infrared spectra (FT-IR), H and 13C NMR, scanning electron microscopy, a mass
spectra method, as well as by Hammett acidity function. The prepared reagent is
efficiently able to catalyze the preparation of 5-arylmethylene-pyrimidine-2,4,6-tri-
ones via the condensation of aldehydes and barbituric acid. Further studies showed
that the condensation of aldehydes with barbituric acid and malononitrile leading to
pyrano[2,3-d]pyrimidinone derivatives can also be efficiently promoted in the pres-
ence of this reagent. The present methodology offers several advantages, including
ease of the preparation and handling of the catalyst, simple and easy work-up, short
reaction times, high yields of the products and recyclability of the catalyst.
Keywords Aldehydes Á Barbituric acid Á 5-Arylmethylene-pyrimidine-2,4,6-
trione Á Pyrano[2,3-d]pyrimidinone Á Succinimidinium N-sulfonic acid hydrogen
sulfate ([SuSA-H]HSO4)
Introduction
Barbituric acid and its derivatives show a varietyof pharmaceutical properties. Among
these types of compounds, arylidene barbituric acids and their 2-thio analogues are
useful intermediates in the synthesis of heterocyclic compounds, benzyl barbituric
derivatives, oxadiazaflavines and unsymmetrical disulphides [1–3].
&
&
1
Masoumeh Abedini
mabedini@guilan.ac.ir
Farhad Shirini
shirini@guilan.ac.ir
Department of Chemistry, College of Science, University of Guilan,
Post Box: 1914, Rasht 41335, Islamic Republic of Iran
123

M. Abedini et al.
5-Arylidenepyrimidine-2,4,6(1H,3H,5H)-trione and pyrano-pyrimidinones, two
important derivatives of barbituric acid, have also received significant attention
from many pharmaceutical and organic chemists, essentially because of the broad
spectrum of their biological and pharmaceutical properties, such as antitumor,
antibacterial, vasodilator, bronchiodilator, antimalarial, antifungal, analgesic, seda-
tive-hypnotic, anti parkinsonian and anti-allergic activities [4–8]. In addition, some
of these compounds have been studied as non-linear optical materials and dyes [9].
Since most of these compounds are colored, they can be used as synthetic dyes and
can gradually replace natural dyes.
There are several reports in the literature for the synthesis of pyrano-
pyrimidinones and 5-arylidene barbituric acid derivatives; these include use of
PVP-Ni nanoparticles [10], CoFe2O4 nanoparticles [11], ethyl ammonium nitrate
(EAN) [12], copper oxide nanoparticles [13], sodium p-toluene sulfonate (NaPTSA)
[14], L-Tyrosine [15], Ce1MgxZr1-xO2 (CMZO) [16], basic alumina [17] and
FeCl3Á6H2O [18] (for the preparation of 5-arylidene barbituric acid derivatives),
KAl(SO4)2Á12H2O [19], L-proline [20], Zn[(L)proline]2 [21], [BMIm]BF4 [22],
tetrabutylammonium bromide (TBAB) [23], (NH4)2ÁHPO4, [24], KBr/Electrolysis
[25], DABCO [26] and sulfonic acid nanoporous silica (SBA-Pr-SO3H) [27]. In
addition, microwave irradiation and mechanochemical methods were also used for
the synthesis of pyrano-pyrimidinones in the absence of catalyst [28, 29].
Although these procedures provide an improvement, some of these catalysts suffer
from disadvantages, such as low yields, long reaction times, harsh reaction conditions,
tedious work-up and the requirement of excess amounts of reagents or catalysts.
Therefore, finding simple, efficient, and mild procedures using easily separable
and reusable catalysts to overcome these problems is still in demand.
N-Sulfonic acids are important catalysts that could be easily prepared by simple
reaction of N-substituted organic compounds with chlorosulfonic acid under mild
conditions. In recent years, an important part of our research has focused on the
preparation, characterization and introduction of different types of these compounds
(e.g., saccharin sulfonic acid (SaSA) [30–32], melamine trisulfonic acid (MTSA) [33–
35], succinimide-N-sulfonic acid (SuSA) [36–38], N-sulfonic acid poly(4-vinylpyri-
dinium) chloride (NSPVPC) [39–42] and succinimidinium hydrogen sulfate ([H-
Suc]HSO4) [43]). The use of prepared reagents in organic reactions showed that these
compounds can be successfully utilized as catalysts in all the studied reactions.
Herein and in continuation of these studies, we wish to report the preparation,
characterization and application of succinimidinium N-sulfonic acid hydrogen
sulfate ([SuSA-H]HSO4) as a new efficient ionic liquid catalyst in the promotion of
the synthesis of 5-arylmethylene-pyrimidine-2,4,6-trione and pyrano[2,3-d]pyrim-
idinone derivatives.
Experimental
Chemicals were purchased from Fluka, Merck, and Aldrich chemical companies.
All yields refer to the isolated products. Products were characterized by comparison
of their physical constants, and also by their infrared (IR) and nuclear magnetic
123

Succinimidinium N-sulfonic acid hydrogen sulfate as an…
resonance (NMR) spectra, with authentic samples and those reported in the
literature. The purity determination of the substrate and reaction monitoring were
accompanied by thin-layer chromatography (TLC) on silicagel polygram SILG/UV
254 plates.
The Fourier transform (FT)-IR spectra were recorded on a Perkin Elmer 781
1
Spectrophotometer. The H NMR spectra were recorded with Bruker Avance 400
instruments. In all cases, the chemical shifts are quoted in parts per million (ppm)
relative to TMS using deuterated solvent. The 13C NMR data were collected on
Bruker Avance 100 MHz instrument. Mass spectrometry (MS) studies were
performed using 5973 network mass selective detector, Agilent Technology (HP)
company (ion source: electroni (EI) 70 eV; ion source temperature: 230 °C;
analyzer: quadrupole). Melting points were recorded on a Bu¨chi B-545 apparatus in
open capillary tubes.
Preparation of [SuSA-H]HSO4
Succinimide-N-sulfonic acid [SuSA] was prepared according to the reported method
in the literature [30]. Then, sulfuric acid 98 % (0.5 mL) was added dropwise to a
mixture of SuSA (1.68 g) in dry CH2Cl2 (10 mL) over a period of 2 min in an ice
bath. The resulting mixture was stirred for 1 h and then the solvent was decanted.
The obtained compound was washed with dry diethylether (2 9 5 mL) and dried
under vacuum to give [SuSA-H]HSO4 as a white gel in 98 % (Scheme 1).
Spectroscopic data for [SuSA-H]HSO4 are as follow:
1
FT-IR (KBr, cm-1) tmax: 3418, 1706, 1294, 1182, 855, 581 cm-1; H NMR
(400 MHz, DMSO-d6): d = 2.49 (4H, s), 7.39 (2H, s), 10.84 (1H, s, OH) ppm; 13
NMR (100 MHz, DMSO-d6) d = 29.78, 180 ppm; MS: 56, 99, 278 m/z.
C
General procedure for the preparation of 5-arylmethylene-pyrimidine-
2,4,6-trione derivatives
A mixture of the aldehyde (1 mmol), barbituric acid (1 mmol) and [SuSA-H]HSO4
(0.02 mmol) in water (3 mL) was stirred at room temperature. After completion of
the reaction, as monitored by TLC, using n-hexane:EtOAc (1:3), the crude product
was filtered off to separate the catalyst, washed with water and recrystallized from
O
O
O
H2SO4, CH2Cl2
0 o C - r.t.,1 h
ClSO3H, CH2Cl2
o C-r.t., 2 h
HSO4
0
NH
N
SO3H
N
SO3H
H
O
O
O
SuSA
[SuSA-H]HSO4
Scheme 1 The preparation of [SuSA-H]HSO4
123

M. Abedini et al.
ethanol to afford the pure compound. After separation of the product, the catalyst
was recovered by evaporation of water, washed with Et2O, dried at 50 °C under
vacuum for 1 h and reused for the same reaction.
General procedure for the preparation of pyrano[2,3-d]pyrimidinones
A mixture of an aldehyde (1 mmol), malononitrile (1 mmol), barbituric acid
(1 mmol) and [SuSA-H]HSO4 (0.05 mmol) in water (3 mL) was stirred in an oil
bath (80 °C) for appropriate time. After completion of the reaction, the solid product
was collected by filtration and recrystallized with ethanol to afford the pure
compounds.
Results and discussion
Succinimidinium N-sulfonic acid hydrogen sulfate ([SuSA-H]HSO4), as new
succinimide-based reagent, was prepared as described in ‘‘General procedure for
the preparation of pyrano[2,3-d]pyrimidinones’’ section. This reagent is character-
1
ized using different methods, including of techniques including FT-IR, H and 13C
NMR, scanning electron microscopy (SEM), a mass spectra method, as well as by
Hammett acidity function.
Catalyst characterization
IR analysis
The infrared spectra of succinimide, SuSA and [SuSA-H]HSO4 are shown in Fig. 1.
The IR spectrum of the ionic liquid shows a broad peak at 3000–3600 cm-1, which
can be related to the OH stretching of the SO3H groups. Moreover, the strong peaks
observed at 581, 882 and 1182 cm-1 correspond to the S–O symmetric and
asymmetric stretchings, respectively. It should be noted that the two peaks of the
carbonyl groups in succinimide, which are observed at 1698 and 17,777 cm-1
converted to one peak (1706 cm-1) in the catalyst [36].
,
1H NMR analysis
The 1H NMR spectra of succinimidinium hydrogen sulfate [Su-H]HSO4 and [SuSA-
H]HSO4 are compared in Fig. 2. In the 1H NMR spectrum of [SuSA-H]HSO4
(Fig. 2a), in addition to the other protons, the acidic hydrogen of HSO4 appears at
10.84 ppm [43]. This observation clarifies that [SuSA-H]HSO4 is exactly synthe-
sized (Fig. 2a).
13C NMR analysis
Furthermore, the 13C NMR spectrum of [SuSA-H]HSO4 is shown in Fig. 3. The
peaks corresponding to carbons of the catalyst are shown in 29.78 and 180.14 ppm.
123

Succinimidinium N-sulfonic acid hydrogen sulfate as an…
Fig. 1 FT-IR spectra of succinimide, SuSA and [SuSA-H]HSO4
Mass analysis
The mass spectrum of [SuSA-H]HSO4 is shown in Fig. 4. In this spectrum, the
correct molecular ion peak appears at 278. Another ion peak is observed at 99
(M?–SO3H and HSO4) [43].
123

M. Abedini et al.
Fig. 2 1H NMR spectra of [SuSA-H]HSO4 (a) and [Su-H]HSO4 (b)
SEM analysis
The samples of succinimide and [SuSA-H]HSO4 were also analyzed by SEM with
various magnifications for determining the particle shape, size distribution and
surface morphology (Fig. 5). These images show that with chemical modification,
the primary morphology of succinimide is completely changed and the particles are
aggregated in the product. This increases the surface area of the catalyst, and finally
its catalytic activity. This aggregation can be caused by hydrogen bonding sites and
nearby positive and negative sides [43].
Hammett acidity
The Hammett acidity method is an effective way to assess the acidity strength of an
acid in organic solvents, using a UV–Vis technique [44]. The Hammett function is
defined as:
123

Succinimidinium N-sulfonic acid hydrogen sulfate as an…
Fig. 3 13C NMR spectra of [SuSA-H]HSO4
Fig. 4 Mass spectra of [SuSA-H]HSO4
À
Á
H0 ¼ pKðIÞaqþ log ½IŠs=½IHþŠ
where the pK(I)aq is the pKa value of aqueous solution of indicator, [IH?]s and [I]s
are the molar concentrations of protonated and unprotonated forms of the indicator
s
123

M. Abedini et al.
Fig. 5 SEM micrographs of [SuSA-H]HSO4 (a–c) and succinimide (d–f)
in the solvent, respectively. According to Lambert–Beer’s Law, the value of [I]s/
[IH?]s can be determined and calculated through UV–visible spectrum.
For this purpose, 4-nitroaniline (pK(I)aq = 0.99) and CCl4 were chosen as the
basic indicator and the solvent, respectively . As can be seen in Fig. 6, the maximal
absorbance of the unprotonated form of the indicator was observed at 330 nm in
CCl4. When [SuSA-H]HSO4 was added to the indicator solution as the ionic liquid
catalyst, the absorbance of the unprotonated form of the indicator decreased, which
indicated that the indicator was partially in the form of [IH?]. These results are
listed in Table 1, and show the acidity strength of [SuSA-H]HSO4.
Fig. 6 Absorption spectra of
4-nitroaniline (indicator) and
[SuSA-H]HSO4 (catalyst) in
CCl4
123

Succinimidinium N-sulfonic acid hydrogen sulfate as an…
Table 1 Calculation of the Hammett acidity function (H0) for [SuSA-H]HSO4
Entry
Catalyst
Amax
[I]s (%)
[IH?]s (%)
H0 [Ref.]
1
2
3
–
1.329
0.412
0.182
100
0
–
SuSA
25.4
13.69
74.6
86.31
0.52 [36]
0.191
[SuSA-H]HSO4
Condition for UV–visible spectrum measurement: solvent: CCl4, indicator: 4- nitroaniline (pK
(I)aq = 0.99), 1.44 9 10-4 mol/L (10 mL); catalyst: [SuSA or [SuSA-H]HSO4 (10 mg), 25 °C
Fig. 7 Titration and the first derivative curves of the ionic liquid with NaOH
Comparison of the Hammett acidity of SuSA (Table 1, entry 2) with [SuSA-
H]HSO4 shows that the prepared ionic liquid is more acidic than SuSA, which may
cause it to be a more efficient catalyst for the requested reactions.
A titration method was used to determine the number of protic protons of the
prepared catalyst. In this experiment, a solution of the ionic liquid was titrated with
NaOH. The titration curve for the reaction of 20.5 mL of 0.09 M ionic liquid with
0.05 M NaOH is given in Fig. 7. This figure clearly shows that, when 110.7 mL of
the basic solution is added, all the acidic protons are neutralized. On the other hand,
Eq. (1) shows that for the neutralization of each of the acidic protons, 36.9 mL of
the basic solution is needed. On the basis of these studies, it can be concluded that
this ionic liquid has three protic protons with almost the same acidic power.
MðacidÞ Â VðacidÞ ¼ MðbaseÞ Â VðbaseÞ
0:09 ðmolarÞ Â 20:5 ðmLÞ ¼ 0:05 ðmolarÞ Â VðbaseÞ
VðbaseÞ ¼ 36:9 mL
ð1Þ
123

M. Abedini et al.
Catalytic activity
On the basis of the information obtained from the above-mentioned studies, we
predicted that [SuSA-H]HSO4 can be used as an efficient catalyst to promote the
reactions, which need an acidic catalyst to speed them up. We were interested in
investigating the applicability of this reagent in the promotion of the synthesis the
barbituric acid derivatives.
To optimize the amount of the catalyst, kind of solvent and temperature, the
reaction of 4-chlorobenzaldehyde (1 mmol) with barbituric acid (1 mmol) was
studied in the presence of [SuSA-H]HSO4 at different conditions, and the results are
tabulated in Table 2. On the basis of these results, optimized conditions were
selected, as shown in Scheme 2.
After optimization of the reaction conditions and in order to study the efficiency
of [SuSA-H]HSO4 in this reaction, various aromatic aldehydes were reacted with
barbituric acid under the selected conditions to furnish the corresponding products
in high yields during short reaction times. The obtained results are summarized in
Table 3. It seems that the nature and electronic properties of the substituent had no
obvious effect on the rate and reaction yields.
After the successful synthesis of a series of 5-arylmethylene-pyrimidine-2,4,6-
trione derivatives, we were interested in extending the applicability of this ionic
Table 2 Optimization of the reaction conditions for the synthesis of 5-arylmethylene-pyrimidine-2,4,6-
trione derivative of 4-chlorobenzaldehyde
Entry [SuSA-H]HSO4 (mmol) Solvent
Time (min) Isolated yield (%) Product
1
2
3
4
5
6
7
0.1
H2O
4
5
98
94
96
95
96
40
40
0.05
0.02
0.1
H2O
H2O
6
H2Oa
EtOH
CH2Cl2
3
Cl
0.02
0.02
0.02
15
30
O
O
HN
HN
O
Solvent-free 30
a
50 °C
O
O
HN
NH
[SuSA-H]HSO4 (0.02 mmol)
H2O, r.t.
NH
HN
+ ArCHO
O
O
O
O
Ar
Scheme 2 [SuSA-H]HSO4 catalyzed the synthesis of 5-arylmethylene-pyrimidine-2,4,6-trione
derivatives
123

Succinimidinium N-sulfonic acid hydrogen sulfate as an…
Table 3 Preparation of 5-arylmethylene-pyrimidine-2,4,6-trione derivatives using [SuSA-H]HSO4 as
the catalyst
Entry Aldehyde
Time Yield Melting point (°C)
Compound
(min) (%)a
Found
Reported [Ref.]
1
2
C6H5CHO
7
6
80
96
263–265
256 [13]
298 [13]
O
HN
O
HN
O
4-ClC6H4CHO
298–299
Cl
O
HN
O
HN
O
3
4
5
3-ClC6H4CHO
2-ClC6H4CHO
4-BrC6H4CHO
6
7
5
93
95
94
273–275
250–252
290–292
274–278 [16]
252 [13]
O
Cl
HN
O
HN
O
O
HN
O
Cl
Br
HN
O
292–293 [13]
O
HN
O
HN
O
6
7
4-FC6H4CHO
6
6
85
96
309–310
270–272
309–310 [13]
272–274 [13]
F
O
HN
O
HN
O
4-NO2C6H4CHO
NO2
O
HN
O
HN
O
8
9
3-NO2C6H4CHO
4-CH3C6H4CHO
8
9
97
98
231–233
280–284
231–232 [13]
282–284 [16]
O
NO2
HN
O
HN
O
Me
O
HN
O
HN
O
10
11
4- CH3OC6H4CHO
2-CH3OC6H4CHO
2
8
85
98
298–300
269–272
306–308 [13]
268–269 [17]
OMe
O
HN
O
HN
O
O
HN
O
OMe
HN
O
123

M. Abedini et al.
Table 3 continued
Entry Aldehyde
Time Yield Melting point (°C)
Compound
(min) (%)a
Found
Reported [Ref.]
12
4-HOC6H4CHO
8
90
[300
[300 [13]
OH
O
HN
HN
O
O
O
13
14
2-HOC6H4CHO
12
3
92
98
249–251
281–282
249–251 [15]
281–282 [16]
HN
HN
O
OH
O
O
4-(CH3)2NC6H4CHO
NMe2
HN
HN
O
O
O
CHO
15
16
a
10
6
90
98
266 (dec) 266 (dec) [10]
HN
HN
O
O
Cinnamaldehyde
266–268
268 [13]
O
NH
O
Ph
NH
O
Isolated yield
O
Ar
O
CN
CN
ArCHO
CN
NH2
[SuSA-H]HSO4 (0.05 mmol)
H2O, 80 oC
HN
+
O
O
N
H
HN
NH
O
O
Scheme 3 [SuSA-H]HSO4 catalyzed the synthesis of pyrano-pyrimidinone derivatives
liquid in the promotion of the preparation of pyrano-pyrimidinone derivatives via
the reaction of aldehyde and malononitrile with barbituric acid under the previously
selected conditions. Our investigations clarified that the synthesis of these types of
compounds can be completed with higher amounts of the catalyst (0.05 mmol) at
80 °C (Scheme 3).
As shown in Table 4, a series of aromatic aldehydes containing either electron-
donating or electron-withdrawing substituent successfully reacted and afforded high
to excellent yields of the pure products under the selected conditions.
123

Succinimidinium N-sulfonic acid hydrogen sulfate as an…
Table 4 Synthesis of pyrano-pyrimidinone derivatives catalyzed by [SuSA-H]HSO4
Entry
Aldehyde
Time (min)
Yield (%)a
Melting point (°C)
Found
Reported [Ref.]
1
C6H5CHO
30
20
20
10
15
20
10
10
13
7
92
95
90
98
98
92
98
95
85
98
95
98
98
215–217
245–247
240–241
211–212
231–233
236–237
267–269
253–256
224–225
204–206
160–162
280–281
231–233
208–210 [29]
239–240 [29]
240–241 [23]
213–215 [29]
230–231 [29]
237–238 [29]
268–270 [21]
262–263 [29]
226–227 [27]
206–208 [19]
162–163 [25]
280–281 [29]
230 [25]
2
4-ClC6H4CHO
3-ClC6H4CHO
2-ClC6H4CHO
4-BrC6H4CHO
4-NO2C6H4CHO
3-NO2C6H4CHO
2-NO2C6H4CHO
4-CH3C6H4CHO
4-HOC6H4CHO
2-HOC6H4CHO
4-CH3OC6H4CHO
4-(CH3)2NC6H4CHO
3
4
5
6
7
8
9
10
11
12
13
a
14
20
15
Isolated yield
Table 5 Comparison of the results obtained from the synthesis of 5-arylmethylene-pyrimidine-2,4,6-
trione and pyrano[2,3-d]pyrimidinone in the presence of [SuSA-H]HSO4with those obtained using other
catalysts
Entry Catalyst loading
(mol%)
Conditions
Time
(min)
Yield (%)
[Ref.]
Product
1
CuO Nps (100 mg)
50 % Aq. NaPTSA
Solvent-free, r.t.
r.t.
7–20
4–15
3–5
92–98 [13]
85–94 [14]
90–94 [16]
73–96 [18]
84–95 [12]
94–80 [11]
80–98 This work
61–90 [27]
80–90 [23]
70–90 [24]
O
Ar
O
2
HN
3
Ce1MgxZr1-xO2 (0.2 gm) M.W.
O
N
H
4
FeCl3Á6H2O (15)
EAN (1 mL)
H2O, reflux
20–50
3–6 h
2–6
5
r.t.
6
CoFe2O4 Nps (1)
[SuSA-H]HSO4 (2)
SBA-Pr-SO3H (10 mg)
TBAB (10)
H2O, EtOH, r.t.
H2O, r.t.
7
2–12
8
Solvent-free, 140 °C 5–45
Ar
O
O
CN
9
H2O, reflux
25–35
HN
10
11
12
13
14
15
16
17
(NH4)2 HPO4 (10)
L-Proline (5)
aq. EtOH, r.t.
aq. EtOH, r.t.
EtOH, reflux
H2O, EtOH, r.t.
H2O, 80 °C
2 h
O
N
H
NH2
30–150 68–86 [20]
Zn[(L)proline]2 (17)
DABCO (10)
30–85
2 h
80–92 [21]
83–96 [26]
Alum (10)
30–45
3–5
80–90 [19]
–
M.W., H2O
86–94 [28]
[BMIm]BF4 (30 mg)
[SuSA-H]HSO4 (5)
Solvent-free, 90 °C
H2O, 80 °C
3–5 h
7–30
82–95 [22]
85–98 (This work)
r.t. Room temperature, M.W. Microwave
123

M. Abedini et al.
Table 5 compares our results with the results reported in the literature using some
of the other catalysts in the synthesis of 5-arylmethylene-pyrimidine-2,4,6-trione
and pyrano[2,3-d]pyrimidinone derivatives.
This comparison indicates that in some of the other methods, the reactions were
completed in the presence of higher amounts of the catalysts and/or during longer
times (Table 5, entries 4, 5, 9, 10, 12, 13, 16). In addition, the main drawbacks in the
application of some of these catalysts are the difficult and time consuming
procedures and/or the use of expensive starting materials (Table 5, entries 1, 6). It is
very important to note that the same reactions in the presence of SuSA and
succinimidinium hydrogen sulfate are completed in longer reaction times.
Finally, to check the reusability of the catalyst, the synthesis of the
requested derivatives of 4-chlorobenzaldehyde (Tables 3, 4, entry 2) under the
optimized reaction conditions were selected as model reactions. After the
separation of the product, the water was evaporated and the catalyst was
washed with Et2O, dried and reused for the same reactions. These process were
carried out over four runs and all reactions led to the desired products with
high efficiency (Fig. 8).
Fig. 8 Recyclability of the [SuSA-H]HSO4 in the reactions reported in Table 3 (up) and Table 4 (down),
entry 2
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Succinimidinium N-sulfonic acid hydrogen sulfate as an…
Conclusion
In this paper, we have developed an efficient, simple and green method for the
synthesis of 5-arylmethylene-pyrimidine-2,4,6-trione and pyrano[2,3-d]pyrimidi-
none derivatives using a new efficient ionic liquid called succinimidinium N-
sulfonic acid hydrogen sulfate which is simply prepared and characterized with a
variety of techniques. Easy preparation of the catalyst, mild and green reaction
conditions, easy work-up procedure, short reaction times and high yields of the
products are significant advantages of this method. Also, this reagent could be
successfully recovered and reused for at least four runs without a significant loss of
activity.
Acknowledgments The authors acknowledge financial support for this work from the Iran National
Science Foundation (INSF) (Grant Number 93014856) and partial support of this work by the Research
Council of the University of Guilan.
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