Nanoammonium salt: a novel and recyclable organocatalyst for one-pot three-component synthesis of 2-amino-3-cyano-4H-pyran derivatives

Article abstract of DOI:10.1007/s13738-017-1127-8

1,3-Propanediaminium methanesulfonate [(PDA)(MeSO₃)] was synthesized as the first nanoaliphatic ammonium salt via a safe and simple chemical route in aqueous media. [(PDA)(MeSO₃)] ammonium salt was characterized by XRD, TEM, SEM, EDS

Full text of DOI:10.1007/s13738-017-1127-8

J IRAN CHEM SOC
DOI 10.1007/s13738-017-1127-8
ORIGINAL PAPER
Nanoammonium salt: a novel and recyclable
organocatalyst for one‑pot three‑component synthesis
of 2‑amino‑3‑cyano‑4H‑pyran derivatives
1
2
2
Moones Honarmand · Atena Naeimi · Mahboobeh Zahedifar
Received: 9 August 2016 / Accepted: 21 April 2017
©
Iranian Chemical Society 2017
Abstract 1,3-Propanediaminium methanesulfonate [(PDA)
MeSO )] was synthesized as the ꢀrst nanoaliphatic ammo-
nium salt via a safe and simple chemical route in aqueous
with certain organic solvents. The widespread range of pos-
sible cation and anion combinations represents the various
applications and tunable interactions [1, 2]. On the other
hand, nanostructural materials due to their unique structural
and textural properties have a broad range of potential uses
in biomedical and biological ꢀelds [3, 4]. Also, the many
reports have been found using nanostructural materials as
efꢀcient catalysts in chemical reactions [5, 6]. To beneꢀt
from the unique properties of molten salts and the valu-
able applications of nanocatalysts, very recently, Zolꢀgol
and his co-workers have been reported the ꢀrst nanomolten
salt, namely 1-methylimidazolium tricyanomethanide [7].
Today’s, the researchers have showed that imidazolium
salts have moderate aquatic toxicity and their industrial
applications are limiting due to expensive cost and high
toxicity [8, 9]. Therefore, other classes of molten salts
require to be analyzed more closely. Among the different
molten salts, ammonium salts are well known and have
wonderful industrial uses due to their bioactivity and sur-
face activity [10–13]. Also, they were easily prepared from
cheap starting materials.
(
3
media. [(PDA)(MeSO )] ammonium salt was character-
3
1
13
ized by XRD, TEM, SEM, EDS, DLS, AFM, H NMR,
C
NMR, FT-IR, TG, and elemental analysis. [(PDA)(MeSO )]
3
ammonium salt was efꢀciently applied as an eco-friendly
and recyclable organocatalyst for the one-pot, three-com-
ponent synthesis of 2-amino-3-cyano-4H-pyran derivatives.
From an economical and environmental point of view, this
novel catalyst has the merits of environmental friendliness,
high yields, shorter reaction time, simple work-up, easy
operation, the avoidance of the organic solvents, and inex-
pensive catalysts.
Keywords Ammonium salt · Nano · Organocatalyst ·
2
-Amino-3-cyano-4H-pyrans · Recyclability
Introduction
In the recent years, molten salts (ionic liquids) have
received signiꢀcant interest in organic synthesis as catalyst
because of their special properties such as low vapor pres-
sure, excellent thermal, chemical stability, nonꢁammability,
tunable polarity, high ionic conductivity, and immiscibility
4H-Pyran and its derivatives represent the key build-
ing blocks of many natural products and constitute the core
of valuable compounds exhibiting a wide range of pharma-
cological and biological activities such as anticancer [14],
antimicrobial [15], antioxidant [16], and antiproliferative
properties [17]. The amino-4H-pyrans are often employed
in pigments and cosmetics, or used as potentially biodegrad-
able agrochemicals. In addition, the 4H-pyran derivatives
bearing a nitrile functional group are useful intermediates for
the synthesis of compounds such as 1,4-dihydropyridines,
pyridones, pyranopyrazoles, imidoesters, aminopyrimidines,
and lactones [18, 19]. Because of the important aforemen-
tioned properties of 4H-pyran derivatives, preparation of
this heterocyclic nucleus has gained great signiꢀcance in
*
Moones Honarmand
honarmand@birjandut.ac.ir; honarmand.moones@yahoo.com
1
Department of Chemical Engineering, Faculty of Mining,
Civil and Chemical Engineering, Birjand University
of Technology, Birjand 97175/569, Iran
2
Department of Chemistry, Faculty of Science, University
of Jiroft, Jiroft, Iran
1
3

J IRAN CHEM SOC
organic synthesis. Several methods have been reported for
the one-pot synthesis of 2-amino-3-cyano-4H-pyran scaf-
fold via a three-component condensation of aldehydes and
alkylmalonates with carbonyl compounds possessing a reac-
tive α-methylene group in the presence of heterogenous and
Scheme 2 Synthesis of 2-amino-3-cyano-4H-pyran derivatives cata-
homogenous catalysts such as PEG-SO H [20], tungstic acid
3
lyzed by [(PDA)(MeSO )] nanoammonium salt
3
functionalized mesoporous SBA-15 [21], nanosized zeolite
clinoptilolite [22], KSF [23], CuO-CeO [24], Mg/Al hydro-
2
talcite [25], cetyltrimethylammonium chloride [26], egg shell
Transform Infrared Spectrophotometer (FT-IR-8300).
A Shimadzu thermogravimetric analyzer (TG-50) was
applied to characterize the gravimetric (TG) behavior of
[27], S-proline [28], alumina [29], KF/Al O [30], imidazole
2 3
[
31], 4-dimethylaminopyridine [32], Et N, piperidine [33],
3
morpholine [34], combined NaOAc/KF [35], tetraalkylam-
monium halides [36] or ionic liquids including [2-AEMIm]
the [(PDA)(MeSO )] ammonium salt. Elemental analysis
3
was carried out by a ECS4010 CHNSO analyzer. Power
X-ray diffraction (XRD) patterns were obtained through
a Bruker D8-advance X-ray diffractometer with Cu Ka
PF [37], TMGT [38], and [cmmim]Br, [cmmim][BF ] [39].
6
4
Although these protocols are valuable, they undergo one or
more of the following disadvantages such as high tempera-
ture, low yields, long reaction times, using a large amount of
toxic catalyst or solvents, and tedious work-up procedures.
Therefore, it is still preferable to follow a green procedure
applying a reusable nonhazardous catalyst for the efꢀcient
synthesis of 2-amino-3-cyano-4H-pyrans.
(
(
k = 0.154 nm) radiation. An atomic force microscopy
DME Model Igloo) was also utilized for AFM images.
Morphologies of [(PDA)(MeSO )] were observed using a
3
scanning electron microscope (JSM-5600LV, JEOL Ltd.,
Japan) with an operating voltage of 3 kV. The elemen-
tal composition of catalyst was analyzed using an X-ray
energy-dispersive spectroscopy (EDS) detector (IE 300X,
Oxford, UK) attached to the SEM. The particle size dis-
tribution of nanoammonium salt was characterized by
In continuing our efforts on the development of envi-
ronmentally benign procedures by using efꢀcient catalysts
[40–45], herein, we have synthesized 1,3-propanediaminium
methanesulfonate [(PDA)(MeSO )] as the ꢀrst nanoaliphatic
3
dynamic light scattering (DLS, VASCO -Cordouan) with
3
ammonium salt in aqueous media (Scheme 1).
cumulants method.
To explore the catalytic activity of [(PDA)(MeSO )]
3
ammonium salt in organic reactions, we have used it as a
recyclable organocatalyst for the efꢀcient one-pot, three-
component synthesis of 2-amino-3-cyano-4H-pyran deriva-
tives (Scheme 2).
Typical procedure for the synthesis of [(PDA)(MeSO )]
nanoammonium salt
3
A solution of methanesulfonic acid (50 mmol, 4.805 g)
in water (30 mL) was dropwisely added to an aqueous
solution of 1,3-diaminopropane (50 mmol, 3.706 g) at
room temperature. However, the stirring of the result-
ant solution was preserved for another 20 h at the same
conditions. Then water was removed by distillation under
reduced pressure, and the residue was dried at room tem-
Experimental section
General information
Chemicals were purchased from Merck Chemical Com-
pany and used as received. Melting points were deter-
mined by Buchi 510 apparatus and are uncorrected.
NMR spectra were recorded on a Bruker Avance DPX-
perature to reach up to [(PDA)(MeSO )] as a shiny white
3
solid.
1,3-Propanediaminium methanesulfonate [(PDA)
4
00 using deutrated DMSO-d and CDCl as solvent and
(MeSO )]. M.P: 157 °C; Yield: 96% (12.78 g); IR (KBr):
6
3
3
−
1
1
TMS as internal standard. The purity of the products and
the progress of the reactions were accomplished by TLC
on silicagel polygram SILG/UV254 plates. TEM analysis
was performed using TEM microscope (Philips CM30).
FT-IR spectra were recorded on a Shimadzu Fourier
υ 3200–2500, 1619, 1318, 1137, 595 cm ; H NMR
(400 MHz, DMSO-d , ppm): δ 7.86 (br, 6 H, NH ), 2.88
6
3
3
(t, J
= 9.6 Hz, 4 H, CH ), 2.42 (s, 6 H, CH ), 1.86 (p,
H–H
2
3
3
13
JH–H = 9.6 Hz, 2 H, CH ); C NMR (100 MHz, DMSO-
2
d ): δ 40.1, 36.5, 25.4.
6
Scheme 1 Synthesis of 1,3-propanediaminium methanesulfonate [(PDA)(MeSO )]
3
1
3

J IRAN CHEM SOC
General procedure for the synthesis
of 2‑amino‑3‑cyano‑4H‑pyran in the presence of [(PDA)
(1 mmol) and carbonyl compound possessing a reactive
α-methylene group (1 mmol). The reaction mixture was
stirred at 60 °C for the appropriate time (Table 2). The pro-
gress of the reaction is monitored by TLC. After comple-
tion of the reaction, water (5 mL) was added to the reac-
tion mixture and the resulted solid ꢀltered and completely
(
MeSO )] nanoammonium salt
3
[
(PDA)(MeSO )] (10 mol%, 0.0266 g) was added to
3
a stirred mixture of aldehyde (1 mmol), malononitrile
1
Fig. 1 a The H NMR spec-
trum of [(PDA)(MeSO )], b The
3
1
3
C NMR spectrum of [(PDA)
MeSO )]
(
3
1
3

J IRAN CHEM SOC
washed with H O (2 × 10 mL). Pure products were
The possibility to use water as a standard “green” solvent
for the synthesis of catalyst as well as a reaction medium
2
obtained by recrystallization in aqueous ethanol. Nanoam-
monium salt was recovered by evaporation of the ꢀltrate
and drying in vacuum at room temperature.
was a salient feature. The synthesized [(PDA)(MeSO )]
3
1
nanoammonium salt was fully characterized by H NMR,
1
3
C NMR, elemental analysis, FT-IR, TGA, XRD, SEM,
TEM, DLS, EDS, and AFM.
Spectral data of 2‑amino‑3‑cyano‑4H‑pyran derivatives
1
13
The H NMR and C NMR spectra of [(PDA)(MeSO )],
3
1
7
‑Amino‑1,3‑dimethyl‑5‑(3‑nitrophenyl)‑2,4‑di‑
in DMSO-d are shown in Fig. 1. The main peaks of H
6
oxo‑1,3,4,5‑tetrahydro‑2H‑pyrano[2,3‑d] pyrimidine‑6‑car‑
bonitrile (23) The colorless crystals, H NMR (400 MHz,
NMR spectrum of [(PDA)(MeSO )] were attributed to NH
3
1
of cationic moiety and CH of anionic moiety detecting
3
4
4
CDCl ): δ 8.15 (d, 1 H, J
= 8 Hz, Ar), 8.14 (d, 1 H, J
in δ = 7.86 and 2.42 ppm, respectively. The presence of a
3
H–H
H–
3
=
1 Hz, Ar), 7.83 (d, 1 H, J
= 8 Hz, Ar), 7.68–7.64
peaks in δ = 1.86 and 2.88 ppm was allocated to hydro-
H
H–H
3
13
(t, 1 H, J
= 8 Hz, Ar), 7.53 (s, 2 H, NH ), 4.63 (s, 1 H,
gens of methylene group. Also, in C NMR spectrum of
H–H
2
CH), 3.42 (s, 3 H, CH ), 3.13 (s, 3 H, CH ) ppm; IR (KBr)
[(PDA)(MeSO )], carbons of anionic moiety were observed
3
3
3
−1
3
335, 3231, 2200, 1689, 1630, 1529, 1513, 1492 cm .
in δ = 40.1 ppm. Two peaks were appeared at δ = 36.5 and
2
5.4 ppm related to carbons of cationic moiety.
FT-IR spectra of [(PDA)(MeSO )], 1,3-diamino pro-
3
7
‑Amino‑5‑(2,4‑dichlorophenyl)‑1,3‑di‑methyl‑2,4
pane and methanesulfonic acid are implied in Fig. 2. In
‑
dioxo‑1,3,4,5‑tetrahydro‑2H‑pyrano
[2,3‑d]
pyrimi‑
the FT-IR spectrum of [(PDA)(MeSO )], a broad peak
centered at 2500–3200 cm was attributed to stretching
3
1
−1
dine‑6‑carbonitrile (25) The yellow crystals; H NMR
(
7
400 MHz, CDCl ): δ 8.09 (s, 2 H, NH ), 7.81 (s, 1 H, Ar),
3 2
3
3
.59 (d, J
= 8 Hz, 1 H, Ar), 7.38 (d, J
= 8 Hz, 1
H–H
H–H
H, Ar), 4.40 (s, 1 H, CH), 3.57 (s, 3 H, CH ), 3.15 (s, 3
3
H, CH ). ppm; IR (KBr): υ 3334, 3236, 2221, 1708, 1660,
3
−
1
1
551, 1513, 1485 cm .
Procedure for the reusability test of [(PDA)(MeSO )]
3
nanocatalyst
[
(PDA)(MeSO )] (10 mol%, 0.0798 g) was added to a stirred
3
mixture of benzaldehyde (3 mmol), malononitrile (3 mmol),
and dimedone (3 mmol). The reaction mixture was stirred at
60 °C for 8 min. Then, water (5 mL) was added to the reac-
tion mixture and the resulted solid ꢀltered and washed with
H O (2 × 10 mL). Nanoammonium salt was recovered by
2
evaporation of the ꢀltrate and drying in vacuum at room tem-
Fig. 2 FT-IR spectra of [(PDA)(MeSO )], 1,3-diamino propane and
methanesulfonic acid
3
perature. [(PDA)(MeSO )] was then reused at the same con-
3
ditions as above for at least ꢀve reaction runs and delivered
the corresponding product (6) in high yield.
Results and discussion
Synthesis and characterization
of 1,3‑propanediaminium methanesulfonate [(PDA)
(
MeSO )] as a nanoammonium salt
3
1
,3-Propanediaminium methanesulfonate [(PDA)(MeSO )]
3
was synthesized as a nanobifunctional ammonium salt
from cheap and readily available starting materials. The
important advantage of the synthesized nanocatalyst was
related to a safe and simple procedure for its preparation.
Fig. 3 Thermal gravimetric (TG) analysis of [(PDA)(MeSO )]
3
1
3

J IRAN CHEM SOC
The thermogravimetric (TG) analysis was used to deter-
mine the thermal stability of [(PDA)(MeSO )] (Fig. 3).
3
According to the TGA, the weight loss of [(PDA)(MeSO3)]
nanoammonium salt was occurred in a single step after 287 °C
was indicative of its good thermal stability up to 287 °C.
Size, shape, and morphology of [(PDA)(MeSO )]
3
as nanoammonium salt were studied through X-ray
diffraction (XRD) pattern, scanning electron micros-
copy (SEM), transmission electron microscopy (TEM),
dynamic light scattering (DLS), energy-dispersive X-ray
spectroscopy (EDS), and atomic force microscopy
(AFM) analysis imaging demonstrations.
Fig. 4 XRD pattern of [(PDA)(MeSO )]
3
XRD patterns of [(PDA)(MeSO )] in a domain of 10°–
3
6
0° are illustrated in Fig. 4. As shown in Fig. 4, XRD pat-
+
vibrations of N–H (NH ) bands. The peak was appeared
terns presented diffraction lines including high crystal-
line nature at 2θ ≈ 17.00°, 25.48°, and 34.27°. The mean
crystallite size was calculated via the Scherrer equation
[D = Kλ/(βcosθ)] (where D is the crystallite size, K is
the shape factor, λ is the X-ray wavelength, β is the full
width at half maximum of the diffraction peak, and θ is
the Bragg diffraction angle in degree) and found to be in
the nanometer range (15.1–31.0 nm).
3
−1
at 1619 cm in the spectra of [(PDA)(MeSO )], and
,3-diamino propane could be related to the bending vibra-
tions of N-H bond. In the spectra of [(PDA)(MeSO )] and
methanesulfonic acid, two absorption peaks at 1318 and
137 cm were well assigned to the stretching vibra-
tions of S=O bond. Also, the presence of a band at around
95 cm was allocated to S–O stretching vibrations. These
3
1
3
−1
1
−1
5
results were indicated that [(PDA)(MeSO )] as ammonium
SEM image and TEM image of [(PDA)(MeSO )] are
3
3
salt was successfully synthesized.
shown in Fig. 5. The particles size distribution of [(PDA)
(
a)
(b)
6
5
4
3
2
1
0
0
0
0
0
0
0
5
10
15
20
25
30
(
c)
Particle size (nm)
Fig. 5 a Scanning electron microscopy (SEM), b transmission electron microscopy (TEM) and c particles size distribution of [(PDA)(MeSO )]
3
1
3

J IRAN CHEM SOC
Energy-dispersive X-ray spectroscopy (EDS) analy-
sis was used for structure identiꢀcation [(PDA)(MeSO )]
3
ammonium salt (Fig. 7) and showed elemental composi-
tion of ammonium salt, including N, C, O, and S in which
the obtained results were of acceptable concordance with
the elemental analysis data (N = 10.54%, C = 22.58%,
H = 6.79% and S = 24.10%).
The AFM images of [(PDA)(MeSO )] were gave good
3
information about surface morphology of nanoammonium
salt. AFM images were derived from 1.1 μm * 1.1 μm
scan part of the samples (Fig. 8). No key division area in
size was identiꢀed in the illustrations. From three-dimen-
2
sional 1.1 μm × 1.1 μm framework, it came out that the
Fig. 6 Size distribution of [(PDA)(MeSO )] by DLS
3
achieved nanostructure ammonium salt showed an inter-
rupted structure with a superior beyond planarity. In the
(
MeSO )] was evaluated using TEM and showed that the
surface conformation of the coat, [(PDA)(MeSO )] was
3
3
mean diameter of nanoparticles was about 15 nm. These
results were in good agreement with the XRD results.
obviously detected with the size distribution 23–26 nm.
The particles size distribution of the [(PDA)(MeSO )]
Catalytic activity of [(PDA)(MeSO )] nanoammonium
3
3
was also investigated by dynamic light scattering (DLS)
technique (Fig. 6). The hydrodynamic diameter of the par-
ticles was obtained in the range of 122–255 nm with the
maximum peak around 164 nm by DLS that was about
ten times larger than that obtained by TEM. This is due to
the fact that the hydrodynamic nanoparticle diameter was
measured in their dispersion situation, whereas TEM ana-
lyzed the particle core. Also, TEM gave the number aver-
age, while DLS provided the z-average of the diameter that
was strongly affected by the presence of large particles
salt in the synthesis of 2‑amino‑3‑cyano‑4H‑pyran
derivatives
The catalytic activity of the prepared nanoammonium salt
was examined through the synthesis of 2-amino-3-cyano-
4H-pyrans. For this purpose, initially, the reaction of ben-
zaldehyde, malononitrile, and dimedone in the presence of
10 mol% of [(PDA)(MeSO )] was chosen as a model reac-
3
tion. The model reaction was investigated for the optimizing
of the solvent, in the presence of different solvents such as
acetonitrile, toluene, ethanol, water, and under solvent-free
[46].
Fig. 7 EDS spectrum of
(PDA)(MeSO )]
[
3
1
3

J IRAN CHEM SOC
conditions at 60 °C (Table 1, entries 1–5). As shown in
Table 1, the best result was obtained under solvent-free con-
ditions. A similar reaction at lower temperatures required
longer reaction time and produced the desired product in
lower yield (Table 1, entry 6). Further, no improvement was
observed by increasing the reaction temperature from 60
to 80 °C in terms of reaction time and yield of the product
(Table 1, entry 7). Similar reactions were performed in the
presence of different catalytic amounts of [(PDA)(MeSO )]
3
at 60 °C under solvent-free conditions (Table 1, entries 8
and 9) and found that 10 mol% of the catalyst, which was
used in the model reaction, was the best amount. The model
reaction was also examined in the absence of the catalyst
and low amount of the desired product obtained after 12 h.
This result showed the importance of the presence of the
catalyst for this reaction.
The generality and versatility of this method for the
synthesis of 2-amino-3-cyano-4H-pyran derivatives were
investigated by the reaction of malononitrile, various
aldehydes and carbonyl compounds possessing a reactive
α-methylene group under optimized reaction conditions
(10 mol% of nanoammonium salt at 60 °C under solvent-
free conditions). The results of these studies are summa-
rized in Table 2.
As indicated in Table 2, the reactions of substituted
benzaldehydes bearing electron-releasing and electron-
withdrawing groups with dimedone and malononitrile
were proceed well and produced the corresponding prod-
ucts in good to high yields in short reaction times (Table 2,
entries 1–5). To further expand the scope of the reaction,
the use of diverse carbonyl compounds possessing a reac-
tive α-methylene group [namely 1,3-cyclohexanedione,
4
6
-hydroxycoumarine, 4-hydroxy-6-methyl-2-pyrone and
-hydroxy-1,3-dimethylpyrimidine-2,4(1H,3H)-dione] was
investigated. To our surprise, all they were easily trans-
formed into the desired products in good to high yields in
short reaction time (Table 2, entries 6–25).
Fig. 8 a Two-dimensional and b three-dimensional AFM topography
images of [(PDA)(MeSO )]
3
Table 1 Synthesis of 2-Amino-
a
Entry
Amount of catalyst (mol%)
Temperature (°C)
Solvent
Time (min)
Yield (%)
4-benzoyl-7,7-dimethyl-5-oxo-
5,6,7,8-tetrahydro-4Hchromene-
3-carbonitrile under different
1
2
3
4
5
6
7
8
9
10
10
10
10
10
10
10
5
60
60
60
60
60
40
80
60
60
60
–
8
95
81
73
79
92
88
95
84
95
10
Acetonitrile
40
120
30
10
120
8
conditions
Toluene
Ethanol
Water
–
–
–
–
–
25
8
20
–
1
0
12 h
a
Isolated yields. Conditions: aldehyde (1 mmol), malononitrile (1 mmol) and dimedone (1 mmol)
1
3

J IRAN CHEM SOC
Table 2 Synthesis of 2-amino-3-cyano-4H-pyran derivatives in the presence of [(PDA)(MeSO )] ammonium salt
3
O
Ar
O
CN
CN
CN
[
(PDA)(MeSO3)] (10 mol%)
+
H C
+
2
Ar
H
Water
O
o
O
NH2
6
0 C
Time Yielda
min) (%)
Mp (ºC)
Entry
Ar
Product
O
(
O
O
CN
1
8
6
95
93
O
O
NH2
1
O
O
O
2
O
CN
O
O
NH2
2
NO2
O
O
3
4
CN
3
4
92
91
NO2
O
O
NH2
3
Cl
O
O
Cl
CN
O
O
NH2
4
Cl
Cl
O
O
Cl
CN
5
3
92
Cl
O
O
NH2
5
1
3

J IRAN CHEM SOC
Table 2 continued
O
O
CN
6
5
7
95
90
O
O
NH2
6
O
O
O
7
O
CN
O
O
NH2
7
NO2
O
O
8
9
CN
3
3
98
93
NO2
O
O
NH2
8
Cl
O
O
Cl
CN
O
O
NH2
9
Cl
Cl
O
O
Cl
CN
1
1
0
1
3
6
94
87
Cl
O
O
NH2
1
0
OH
O
CN
O
O
O
O
NH2
11
1
3

J IRAN CHEM SOC
Table 2 continued
O
O
OH
O
O
O
1
2
O
10
82
90
86
CN
O
O
O
NH2
1
2
NO2
OH
O
CN
1
1
3
4
4
O
NO2
O
NH2
1
3
Cl
OH
O
O
5
Cl
CN
O
O
O
NH2
1
4
Cl
Cl
OH
O
O
Cl
CN
1
1
5
6
4
7
88
88
82
Cl
O
O
O
NH2
1
5
OH
O
CN
O
O
O
O
NH2
16
O
OH
O
O
1
7
O
12
CN
O
O
O
NH2
17
1
3

J IRAN CHEM SOC
Table 2 continued
NO2
OH
O
O
O
O
CN
1
8
5
92
O
NO2
O
O
NH2
18
Cl
OH
O
19
6
90
Cl
CN
O
O
O
NH2
19
Cl
Cl
OH
O
Cl
20
5
90
CN
Cl
O
O
O
NH2
20
O
N
O
OH
O
N
CN
21
7
85
N
N
O
O
NH2
21
O
O
N
O
OH
O
N
2
2
2
3
O
15
80
89
N
CN
N
O
O
NH2
22
NO2
O
N
O
N
O
OH
CN
N
5
N
NO2
NH2
O
O
2
3
1
3

J IRAN CHEM SOC
Table 2 continued
Cl
O
O
N
O
OH
O
N
2
4
6
85
87
Cl
N
CN
N
O
NH2
24
Cl
Cl
O
N
O
OH
O
N
Cl
CN
2
5
4
N
N
Cl
O
O
NH2
25
a
Isolated yields. Conditions: aldehyde (1 mmol), malononitrile (1 mmol), carbonyl compound possessing a reactive α-methylene group
(
1 mmol), [(PDA)(MeSO )] (10 mol%), 60 °C, solvent-free conditions
3
The recovery of [(PDA)(MeSO )] ammonium salt in
3
the reaction of benzaldehyde, malononitrile and dime-
done was investigated in the presence of nanocatalyst
(
10 mol%) at 60 °C under solvent-free conditions. The
reaction was very clean and the desired product obtained
in excellent yield. After the completion of the reaction,
since [(PDA)(MeSO )] was completely soluble in water,
3
water was subsequently added to the reaction mixture and
the desired product ꢀltered off and puriꢀed by recrystalli-
zation in ethanol. The nanoammonium salt was recovered
after the evaporation of the ꢀltrate. Therefore, nanoam-
monium salt could be completely isolated easily from the
reaction mixture by simple ꢀltration and reused for ꢀve
cycles without signiꢀcant loss in its activity (Fig. 9).
The comparison of TEM images and DLS of the used
Fig. 9 Recycling experiment of [(PDA)(MeSO )]
3
(
Figs. 10, 11) with fresh catalyst (Figs. 5, 6) showed that
the morphology and particle size of [(PDA)(MeSO )]
3
remained somewhat unchanged after ꢀve recovery times.
Furthermore, the elemental analysis data (CHNS) con-
ꢀ
rmed the accuracy of the recovered catalyst.
The title methodology was cost-effective, environmen-
tally friendly, and industrially important because of using
reusable, eco-friendly, and inexpensive catalyst. These
advantages for this high yielding condensation method
offered ready scalability. For example, in the present
investigation, the condensation of benzaldehyde, malon-
onitrile, and dimedone in a 20 mmol scale in the presence
of the [(PDA)(MeSO )] nanocatalyst was investigated. As
Fig. 10 TEM image of [(PDA)(MeSO )] after ꢀve recovery times
3
3
1
3

J IRAN CHEM SOC
5.
6.
7.
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3
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13. F.S. Xiao, L. Wang, C. Yin, K. Lin, Y. Di, J.L. Prof, R.X. Prof,
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‎
3
expected, the reaction proceeded similarly to the smaller
scale, and the desired product was obtained at the same
isolated yield and reaction time.
14. J.Y.C. Wu, W.F. Fong, J.X. Zhang, C.H. Leung, H.L. Kwong,
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1
1
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(
Conclusions
In summary, in this work, 1,3-propanediaminium meth-
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anesulfonate [(PDA)(MeSO )] was synthesized as a novel
bifunctional ammonium salt in water from cheap and read-
Med. Chem. 44, 3805 (2009)
3
1
9. Y.M. Litvinov, A.M. Shestopalov, Synthesis, structure, chemi-
cal reactivity, and practical signiꢀcance of 2-amino-4H-pyrans,
in Advances in Heterocyclic Chemistry, vol. 103, ed. by A.R.
Katritzky (Academic Press, New York, 2011), pp. 175–260
ily available starting materials. The [(PDA)(MeSO )] was
3
fully characterized by various techniques. Catalytic appli-
cation of [(PDA)(MeSO )] as a recyclable and environ-
20. S. Paul, S. Ghosh, P. Bhattacharyya, A.R. Das, RSC Adv. 3,
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3
1
mentally friendly nanocatalyst was studied in the one-pot,
three-component synthesis of 2-amino-3-cyano-4H-pyran
derivatives at 60 °C under solvent-free conditions. The
most important advantages of this study were high yields,
cleaner reaction proꢀle, short reaction time, the avoidance
of the organic solvents, and easy work-up. In addition to
the above-mentioned advantageous, the use of a recyclable
nanocatalyst was environmentally benign and cost-effec-
tive which made our methodology proper for the industrial
goals.
2
(
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2
2
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2
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