Fabrication, identification and application of Fe3O4 bonded nicotinic acid-sulfonic acid chloride as a retrievable magnetic nanostructured catalyst for the one-pot synthesis of 1-carbamato-alkyl-2-naphthols

Article abstract of DOI:10.1007/s11164-018-3462-5

Abstract: In the presented work, Fe₃O₄ bonded nicotinic acid-sulfonic acid chloride (Fe₃O₄@nicotinic acid @sulfonic acid chloride), as a magnetic reusable catalyst, was prepared by a simple procedure. The identi

Full text of DOI:10.1007/s11164-018-3462-5

Res Chem Intermed
https://doi.org/10.1007/s11164-018-3462-5
Fabrication, identification and application of Fe3O4
bonded nicotinic acid-sulfonic acid chloride
as a retrievable magnetic nanostructured catalyst
for the one-pot synthesis of 1-carbamato-alkyl-2-
naphthols
Ardeshir Khazaei1 Mahsa Tavasoli1 Ahmad Reza Moosavi-Zare2
•
•
Received: 31 December 2017 / Accepted: 4 May 2018
Ó Springer Science+Business Media B.V., part of Springer Nature 2018
Abstract In the presented work, Fe3O4 bonded nicotinic acid-sulfonic acid chloride
(Fe3O4@nicotinic acid @sulfonic acid chloride), as a magnetic reusable catalyst, was
prepared by a simple procedure. The identification of Fe3O4@nicotinic acid @sulfonic
acid chloride was studied by Fourier transform infrared spectroscopy, X-ray diffraction,
thermal gravimetric analysis, scanning electron microscopy, energy dispersive X-ray
analysis and vibrating sample magnetometry. Fe3O4@nicotinic acid @sulfonic acid
chloride was employed as an efficient and heterogeneous catalyst for the one-pot syn-
thesis of some 1-carbamato-alkyl-2-naphthol derivatives in high yields under solvent-
free conditions. Simple work up, high yields, short reaction times and easy recovery of
catalyst are some advantages of this work.
Electronic supplementary material The online version of this article (https://doi.org/10.1007/s11164-
018-3462-5) contains supplementary material, which is available to authorized users.
&
Ardeshir Khazaei
Khazaei_1326@yahoo.com
1
2
Faculty of Chemistry, Bu-Ali Sina University, Hamedan 6517838683, Iran
Department of Chemistry, Sayyed Jamaleddin Asadabadi University, Asadabad 6541861841,
Iran
123

A. Khazaei et al.
Graphical Abstract
Keywords Fe3O4@nicotinic acid @sulfonic acid chloride Á Fe3O4
nanoparticle Á 1-Carbamato-alkyl-2-naphthol Á Solvent-free
Introduction
Nanoparticles are widely used in various pharmaceutical and electronic industries
and in the coloring industry due to their different sizes, shapes and materials. Today,
the application of nanoparticles has been much considered in catalytic applications.
Nanoparticles are desirable substrates to replace homogeneous catalysts. When the
size of the substrate is decreased to nanoscale, the surface-to-volume ratio is
increased. As a result, the activity of stabilized catalysts on nanoparticles increases
because of the interaction of these catalysts with high availability surfaces [1–3].
However, the easy separation and recovery of nano-catalysts from the reaction
environment is still a challenge. Previous reported techniques such as straightening
are not effective for separating these catalysts due to nanoscale particle size. It
involves high cost, long time spent, and the use of special separation techniques
such as centrifugation and chromatography.
In this case, Fe3O4 nanoparticles have been used as an efficient solid support for
catalysts; due to their insoluble and magnetic properties. In addition, the separation
of these compounds from the reaction mixture can be easily done with an external
magnet, where the catalysis filtration is not necessary [4–9].
Recently, most of the chemists are interested in synthesis of organic compounds
using multi component reactions (MCRs). Some advantages of this method are as
follows: Preparing target compounds with high atomic economy and more
efficiency by the reaction of three or more compounds together in one pot,
increasing simplicity and synthetic efficiency of the conventional organic transfor-
mations [10–16].
1-Carbamato-alkyl-2-naphthols are interesting for chemists because of the
biological activities of these compounds. The derivatives of these compounds have
hypotensive and bradycardic effects [17, 18]. Many catalysts have been reported for
the preparation of 1-carbamato-alkyl-2-naphthols by one-pot synthesis between
123

Fabrication, identification and application of Fe3O4…
alkyl carbamates, 2-naphthol and various aromatic aldehydes [19–29]. Some of
these catalysts have some disadvantages such as hard reaction conditions, long
reaction times, low yields, use of corrosive and expensive materials, boring work up
and high reaction temperature. Having the above facts, finding an efficient method is
still needed.
Herein, we have introduced Fe3O4@nicotinic acid @sulfonic acid chloride
nanoparticles as a highly active catalyst for the one-pot synthesis of 1-carbamato-
alkyl-2-naphthols (Scheme 1). Mild and solvent-free conditions, reusable processes,
simple operation, short reaction times, easy recovery, and high yields are some
advantages of this work. The separation of Fe3O4@nicotinic acid @sulfonic acid
chloride from reaction mixture was done by an external magnet and reused for four
times without a significant decrease of the yield.
Experimental
Materials and methods
All of the starting materials and solvents that have been used in this research were
purchased from the Merck Company and were applied without any further
purification. Fourier transform infrared (FT-IR) spectra were recorded using KBr
Pill on a Perkin-Elmer Spectrum 65 .A FT-IR spectrometer in the range of
400–4000 cm-1 was used in order to identify the functional groups in synthesized
1
materials. The H NMR and 13C-NMR spectrums of synthesized products were
identified by 250 MHz Bruker Avance, Switzerland. The determination of the
melting points was done on Bu¨chi B-545 melting points equipment. The crystalline
structure of synthesized catalyst was investigated by X-ray diffraction (XRD) using
an Ital structure APD 2000 with Cu Ka radiation in the 2h range of 10.5–90° at
ambient temperature. Thermal gravimetric analysis (TGA) was reported in the
temperature range of 30–600 °C under nitrogen atmosphere and on a Perkin Elmer
instrument (Model: Pyris 1). It should be noted that the rate of increase in the
temperature is 10 °C/min in this apparatus. To provide elemental identification and
quantitative compositional information of catalyst, the EDX was done using an
Oxford scanning electron microscope instrument. To investigate the surface
morphology of nano-catalyst, FE-SEM was carried out on a SIGMA VP-500
OH
OH
nano catalyst
solvent free, 80 oC
O
+
O
R
NH
NH2
O
R
R=
H
O
O
Aryl
Scheme 1 The preparation of 1-carbamato-alkyl-2-naphthols by nano catalyst
123

A. Khazaei et al.
(ZEISS) instrument. The measurement of super magnetic properties of catalyst was
performed using a vibrating sample magnetometer (MDKB instrument).
Synthesis of nano Fe3O4@Nicotinic acid
Fe3O4@Nicotinic acid was prepared using the previous method [30] as follows: In a
three-necked round-bottom flask, FeCl3Á6H2O (0.0216 mol, 5.89 g), FeCl2Á4H2O
(0.011 mol, 2.17 g) and nicotinic acid (0.043 mol, 5.29 g) were dissolved in
100 mL of distilled water at room temperature. The homogeneous solution is stirred
using a magnetic stirrer under nitrogen atmosphere at 60 °C for 30 min. Then, by
adding 25% solution of NH3 (15 mL) to this mixture, a black colored suspension
appeared. Then the mixture was refluxed under N2 atmosphere at 90 °C for 6 h. In
the end, the resulting black precipitate was separated by an external magnetic field,
and it was washed with distilled water for five times. The obtained nanoparticles
were dried at 60 °C for 12 h.
Synthesis of Fe3O4@nicotinic acid @sulfonic acid chloride nanoparticles
Nano Fe3O4@Nicotinic acid (0.5 g) was added to 6 mL of dry dichloromethane
(under sonication for 30 min) and then added slowly in a 50 mL round-bottomed
flask containing a solution of chlorosulfonic acid (15 mmol) in dichloromethane
(10 mL) and stirred for 3 h. Then, a brown powder was separated by a permanent
magnet, washed thoroughly with dichloromethane for several times and dried at
60 °C for 12 h.
General procedure for solvent free synthesis of 1-carbamato-alkyl-2-
naphthols
A mixture of 2-naphthol (2.0 mmol), benzyl carbamate (2.2 mmol), aromatic
aldehyde (2.0 mmol) and Fe3O4@nicotinic acid @sulfonic acid chloride nanopar-
ticles (0.02 g) as a nanostructured magnetic catalyst was stirred magnetically at 80
8C in an oil bath for an appropriate time. The completion of the reaction was
monitored by TLC. Hot ethyl acetate was added to reaction vessel in order to
dissolve the reaction mixture. The catalyst was separated easily by an external
magnet. After recrystallization, pure crystals of 1-carbamato-alkyl-2- naphthol
derivatives were obtained. The products were identified by spectral and physical
data. The recovered catalyst was washed with hot ethyl acetate for several times,
and dried to reuse for another reaction. The recovered catalyst was used again for
four times on the synthesis of 1-carbamato-alkyl-2-naphthol derivatives without a
significant decrease in the yield of products. The obtained products were identified
1
by H NMR, 13C NMR and FT-IR analysis.
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Fabrication, identification and application of Fe3O4…
Analytical data of selected products
Benzyl ((2-hydroxynaphthalen-1-yl)(phenyl)methyl)carbamate (1a)
M. P. 185–187 °C. IR (KBr, m, cm-1): 3424, 3210, 3067, 1676, 1631, 1516, 1439,
1328, 1271, 1229, 1131, 1041, 944, 808, 753, 697; 1HNMR (250 MHz DMSO-d6, d,
ppm): d 5.046 (s, 2H, CH2), 6.881 (s, 1H, CH), 7.218–7.767 (m, 16H, ArH), 7.882
(s, 1H, NH,), 10.111 (s,1H,OH); 13CNMR (62.9 MHz DMSO-d6, d, ppm): 50.858,
66.131, 118.888, 119.249, 122.960, 123.530, 126.446, 126.814, 126.950, 128.221,
128.545, 128.772, 129.001, 129.777, 132.489, 137.425, 142.758, 153.341, 156.491.
Benzyl ((3-chlorophenyl)(2-hydroxynaphthalen-1-yl)methyl)carbamate (2a)
M. P. 182–186 °C. IR (KBr, m, cm-1): 3436, 3245, 3069, 1675, 1629, 1596, 1508,
1439, 1328, 1272, 1228, 1066, 948, 892, 813, 702; 1HNMR (250 MHz DMSO-d6, d,
ppm): d 5.023 (d, 1H, CH, J = 12.5 Hz), 5.104 (d, 1H, CH, J = 12.5 Hz) 6.89 (d,
1H, CH, J = 7.75 Hz), 7.150–7.779 (m, 15H, ArH), 7.894 (s, 1H, NH), 10.189 (s,
1H, OH); 13CNMR (62.9 MHz DMSO-d6, d, ppm): 50.489, 66.228, 118.648,
118.864, 123.060, 123.341, 125.246, 126.201, 126.818, 127.149, 128.233, 128.777,
129.080, 130.114, 130.463, 132.378, 133.367, 137.373, 145.521, 153.462, 156.548.
Benzyl ((2,4-dichlorophenyl)(2-hydroxynaphthalen-1-yl)methyl)carbamate (3a)
M. P. 205–207 °C. IR (KBr, m, cm-1): 3417, 3344, 3069, 1686, 1628, 1585, 1513,
1
1436, 1341, 1271, 1244, 1054, 845, 820, 744; HNMR (250 MHz DMSO-d6, d,
ppm): d 5.011(s, 2H, CH2), 6.810 (s, 1H, CH), 7.074–7.747 (m, 14H, ArH),
7.965–8.053 (d, 1H, NH, J = 22 Hz), 9.899 (s, 1H,OH); 13CNMR (62.9 MHz
DMSO-d6, d, ppm): 49.893, 65.885, 116.671, 118.982, 122.833, 123.096, 126.918,
127.075, 127.905, 128.137, 128.712, 129.020, 129.081, 130.178, 131.666, 132.416,
132.998, 133.619, 137.532, 139.209, 154.016, 156.070.
Benzyl ((2-hydroxynaphthalen-1-yl)(3-nitrophenyl)methyl)carbamate (4a)
M. P. 201–203 °C. IR (KBr, m, cm-1): 3414, 3306, 3064, 1697, 1630, 1528, 1516,
1441, 1347, 1281, 1048, 811, 696; 1HNMR (250 MHz DMSO-d6, d, ppm): d 5.03(d,
1H, CH, J = 12.5 Hz), 5.11 (d, 1H, CH, J = 12.5 Hz), 6.97 (d, 1H, CH,
J = 8.25 Hz), 7.185–8.053 (m, 15H, ArH), 8.121 (s, 1H, NH), 10.241 (s, 1H,
OH); 13CNMR (62.9 MHz DMSO-d6, d, ppm): 50.497, 66.278, 118.236, 118.838,
120.944, 121.945, 123.129, 123.177, 127.287, 128.193, 128.261, 128.790, 129.130,
130.138, 130.395, 132.340, 133.259, 137.322, 145.428, 148.197, 153.601, 156.641.
Benzyl ((2-hydroxynaphthalen-1-yl)(4-nitrophenyl)methyl)carbamate (5a)
M. P. 203–205 °C. IR (KBr, m, cm-1): 3411, 3306, 3064, 1687, 1628, 1606, 1515,
1
1347, 1276, 1238, 1049, 852, 824, 745; HNMR (250 MHz DMSO-d6, d, ppm): d
5.070 (t, 2H, CH2), 6.97 (d, 1H, CH, J = 7.75 Hz), 7.194–7.963 (m, 15H, ArH), 8.11
123

A. Khazaei et al.
(d, 1H, NH, J = 7.75 Hz), 10.195 (s, 1H, OH); 13CNMR (62.9 MHz DMSO-d6, d,
ppm): 50.724, 66.329, 118.349, 118.820, 123.089, 123.268, 123.762, 127.226,
127.586, 128.248, 128.769, 129.095, 130.355, 132.361, 137.271, 146.529, 151.075,
153.571, 156.635.
Benzyl ((4-bromophenyl)(2-hydroxynaphthalen-1-yl)methyl)carbamate (8a)
M. P. 180–182 °C. FT-IR (KBr, m, cm-1): 3425, 3196, 3069, 1682, 1628, 1517,
1486, 1329, 1273, 1069, 1009, 817, 748; 1HNMR (250 MHz DMSO-d6, d, ppm): d
5.00 (d, 1H, CH, J = 12.75 Hz), 5.07 (d, 1H, CH, J = 12.75 Hz), 6.831 (d, 1H, CH,
J = 8.5 Hz), 7.128–7.801 (m, 15H, ArH), 7.843 (s, 1H, NH), 10.140 (s, 1H, OH);
13CNMR (62.9 MHz DMSO-d6, d, ppm): 50.389, 66.183, 118.75, 118.830, 119.851,
123.002, 123.412, 127.038, 128.216, 128.733, 129.035, 129.990, 131.390, 132.364,
137.349, 142.311, 153.397, 156.485.
Results and discussion
Synthesis and identification of Fe3O4@nicotinic acid @sulfonic acid
chloride
In this work, we report the fabrication of Fe3O4@nicotinic acid @sulfonic acid
chloride nanoparticles, and its catalytic application on the synthesis of 1-carbamato-
alkyl-2-naphthols. The structure of the catalyst was studied by IR, XRD, SEM,
TGA, VSM and EDX analysis. According to the procedure that is shown in
Scheme 2, the catalyst was synthesized in two steps. Firstly, Fe3O4@nicotinic acid
was prepared by refluxing method of iron (II), iron (III) ions and nicotinic acid and
then adding to an aqueous solution of ammonia. Secondly, Fe3O4@nicotinic acid
was functionalized by ClSO3H to produce Fe3O4@nicotinic acid @sulfonic acid
chloride as reusable magnetic catalyst.
The FT-IR spectra of the nicotinic acid (a), Fe3O4@nicotinic acid (b), and
Fe3O4@ nicotinic acid @sulfonic acid chloride nanoparticles (c) were recorded and
shown in Fig. 1. The comparison between FT-IR spectra of nicotinic acid, and
Fe3O4@ nicotinic acid showed that the C=O stretching bond of the carboxyl group,
which appeared at 1711 cm–1 in the pure nicotinic acid, was not present in the
spectrum of Fe3O4@nicotinic acid because of the binding of the nicotinic acid to the
surface of Fe3O4. In Fig. 1b, the observed peak at 1403 cm–1 is due to symmetrical
connection of carboxylic acid oxygen atoms to the surface of Fe3O4 nanoparticles
[31, 32] and also the peak that appeared at 1628 cm–1 corresponded to C=N
vibration of the pyridine ring. Thus, Fe–O bond vibration of iron oxide at 593 cm-1
is shown in Fig. 1b. In the spectrum of Fe3O4@ nicotinic acid@ sulfonic acid
chloride (c), the assigned peak at 3415 cm–1 was related to OH stretching of the
SO3H group. Additionally, spectrum (c) showed the bonds at 1032 and 1133 cm-1
correspond to N-SO2 and O-SO2 vibrations, respectively.
To investigate the crystalline nature and surface state of Fe3O4@ nicotinic acid@
sulfonic acid chloride nanoparticles, X-ray diffraction analysis (XRD) was studied
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Fabrication, identification and application of Fe3O4…
N
N
N
H
O
O
O
O
O
O
O
O
O
N
N
O
O
O
O
e
F
3O4
e
.
+
e
.
Cl2 2O
4H
F
H
F
Cl6 3 2O
NH OH N 90 oC 6
N
h
,
,
2
,
4
O
O
O
O
O
N
N
N
C
l
S
O
3
H
,
d
r
y
C
H
2
C
l
2
Cl
H
SO3
N
Cl
H
O
SO3
Cl
N
N
H
SO3
O
O
O
O
H
O3S
O
Cl
N
O
O
e
F
3O4
Cl
O
O
N
H
SO3
O
O
Cl
O
O
O
O
N
H
O3S
N
Cl
N
H
O3S
H
O3S
Cl
Scheme 2 The synthesis of Fe3O4@nicotinic acid @sulfonic acid chloride
in a domain of 10.5–90°, and the results are shown in Fig. 2. According to Scherer’s
formula, the size of the crystals is calculated from 15 to 90 nm. X-ray diffraction
pattern and FT-IR spectrum of Fe3O4 in comparison with other species of the
catalyst are given in the supporting information (Figures S1 and S2).
123

A. Khazaei et al.
Fig. 1 FT-IR spectra: a nicotinic acid; b Fe3O4@nicotinic acid; c Fe3O4@nicotinic acid @sulfonic acid
chloride nanoparticles
20
15
10
5
0
10.5
30.5
50.5
70.5
2θ (degree)
Fig. 2 X-ray diffraction pattern of Fe3O4@nicotinic acid @sulfonic acid chloride nanoparticles
Thermal gravimetric analysis (TGA) curves of Fe3O4@ nicotinic acid (a) and
Fe3O4@ nicotinic acid@ sulfonic acid chloride (b) are shown in Fig. 3. According
to Fig. 3a, the weight losses of Fe3O4@nicotinic acid was done in two steps. The
first weight loss up to 100 °C could be related to exit solvent from the catalyst. The
thermal decomposition of the organic moiety established on the Fe3O4 surface,
appeared at 260–481 °C at about 5.5%. Also, the Fig. 3b shows a very severe
weight loss in the range of 242–680 °C which represents the stability of the nano-
catalyst in this temperature range.
The measurement of magnetic properties of Fe3O4@nicotinic acid (a), and
Fe3O4@ nicotinic acid@ sulfonic acid chloride nanoparticles (b) was investigated
by VSM at room temperature (Fig. 4). The evaluation of these two curves showed
that the saturation magnetization was reduced from 55 to 12 emu g-1 due to the
functionalization of nicotinic acid by ClSO3H.
123

Fabrication, identification and application of Fe3O4…
Fig. 3 The TG curves: a Fe3O4@nicotinic acid; b Fe3O4@nicotinic acid @sulfonic acid chloride
nanoparticles
The presence of elements such as carbon (C), nitrogen (N), oxygen (O), sulfur
(S), chlorine (Cl) and iron (Fe) was confirmed by an energy-dispersive X-ray (EDX)
spectrum (Fig. 5). The EDX data well demonstrated the synthesis of Fe3O4@
nicotinic acid@ sulfonic acid chloride nanoparticles.
The morphology and the size of the nanostructured catalyst were evaluated by
SEM analysis. These results showed that Fe3O4@ nicotinic acid@ sulfonic acid
chloride nanoparticles appeared uniform, and the size of them is between 11 and
34 nm (Fig. 6).
123

A. Khazaei et al.
Fig. 4 Magnetization curves: a Fe3O4@Nicotinic acid; b Fe3O4@nicotinic acid @sulfonic acid chloride
nanoparticles
123

Fabrication, identification and application of Fe3O4…
Fig. 5 EDX spectrum of Fe3O4@nicotinic acid @sulfonic acid chloride nanoparticles
Fig. 6 SEM image of Fe3O4@nicotinic acid @sulfonic acid chloride nanoparticles
123

A. Khazaei et al.
Catalytical application of Fe3O4 bonded nicotinic acid-sulfonic acid chloride
We have checked the efficacy of the catalyst for the synthesis of 1-carbamato-alkyl-
2-naphthols. The reaction between benzyl carbamate, benzaldehyde and 2-naphthol
undersolvent-free conditions was selected as a model reaction. At first, the reaction
between benzyl carbamate, benzaldehyde and 2-naphthol was done in the absence
of the catalyst over a period of 60 min, but the yield of product was low (Table 1,
Entry 1). The high yield of product was obtained with 0.02 g of catalyst at 80 8C
under solvent-free conditions (Table 1-Entry 6).
The comparisons between this catalyst and the other previous reported catalysts
for the preparation of compound 1a are depicted in Table 2. According to Table 2,
the presented catalyst is more effective than the other reported catalysts in order to
secure shorter reaction time, higher yield, more suitable temperature and easy
recovery.
The generality of the catalyst was investigated by the reaction of various
aromatic aldehydes with 2-naphthol and benzyl carbamate using 0.02 g of the
catalyst under mild reaction conditions (Table 3). The synthesis of 1-carbamato-
alkyl-2-naphthol derivatives with different aldehydes in the presence of Fe3O4@
nicotinic acid@ sulfonic acid chloride had good and acceptable results.
According to previous literature [20, 22, 24, 28, 29], we suggest a possible
mechanism for the synthesis of 1-carbamato-alkyl-2-naphthols catalyzed by
Fe3O4@ nicotinic acid@ sulfonic acid chloride nanoparticles (Scheme 3). In the
initial step, the intermediate (A) was formed by the reaction of 2-naphthol with an
activated aldehyde by the catalyst. Then, by leaving one molecule of H2O from the
intermediate (A), ortho-quinone methide (o-QM) (B) was prepared. Finally, the
Table 1 Effect of different amounts of the catalyst and temperature on the reaction of benzaldehyde
(2 mmol), benzyl carbamate (2.2 mmol) and 2-naphthol (2 mmol) in the absence of solvent
Entry
Catalyst (mol%)
Temperature (°C)
Time (min)
Yield (%)a
1
–
80
80
80
80
80
80
80
80
rt
60
15
15
12
8
Trace
40
50
55
65
88
85
89
30
45
74
88
87
2
0.001
0.005
0.007
0.01
0.02
0.03
0.05
0.02
0.02
0.02
0.02
0.02
3
4
5
6
4
7
4
8
4
9
60
15
7
10
11
12
13
50
70
90
100
4
5
aIsolated yield
123

Fabrication, identification and application of Fe3O4…
Table 2 Comparison result of Fe3O4@nicotinic acid @sulfonic acid chloride nanoparticles with other
reported catalysts in the synthesis of compound 1a
Entry Catalyst
Temperature
(°C)
Time
(min)
Yield
(%)b
References
1
2
3
4
5
6
Al(MS)3Á4H2O
4-(1-Imidazolium) butanesulfonate
70
36
120
10
20
50
4
85
75
75
81
89
88
[19]
[20]
[22]
[25]
[26]
80
NaHSO4/SiO2
100
100
75–80
80
Mg(OOCCF3)2
TweenÒ20
c
–
Fe3O4@ nicotinic acid@ sulfonic acid
chloride
aReaction condition: benzaldehyde (2 mmol), benzyl carbamate (2.2 mmol) and 2-naphthol (2 mmol),
solvent free
bIsolated yield
cThis work
desired 1-carbamato-alkyl-2-naphthol was prepared by the Michael reaction
between benzyl carbamate and orthoquinone methide.
Recovery and reusability of nano-catalyst
To investigate the stability of the catalyst, the reaction between benzaldehyde
(2 mmol), benzyl carbamate (2.2 mmol) and 2-naphthol (2 mmol) was studied as a
model reaction using 0.02 g catalyst at 80 °C under solvent-free conditions. After
completion of the reaction, hot ethyl acetate was added to the reaction mixture and
stirred for 5 min. Then, the catalyst was easily separated by the external magnet.
The separated catalyst was washed with hot ethyl acetate for several times, dried
and reused for another reaction. The catalyst was successfully reused for four times
without any remarkable reducing of catalytic activity (Fig. 7). The FT-IR spectrum
of a reused catalyst was compared with fresh catalyst for which they have high
compliance with each other (Fig. 8).
Conclusions
In this study, we have synthesized Fe3O4 bonded nicotinic acid-sulfonic acid
chloride (Fe3O4@nicotinic acid @sulfonic acid chloride) as a novel heterogeneous
catalyst and fully characterized by various techniques. The catalytic activity of this
catalyst was checked by the one-pot synthesis of 1-carbamato-alkyl-2-naphthol
derivatives under solvent-free conditions. This work showed notable advantages
such as short reaction times, high yields, easily separation and retrievable of the
catalyst.
123

A. Khazaei et al.
Table 3 The solvent-free preparation of 1-carbamato-alkyl-2-naphthols from aromatic aldehydes benzyl
carbamate, and 2-naphthol using Fe3O4@nicotinic acid @sulfonic acid chloride nanoparticles
Entry
1a
Product
Time (min)
Yield (%)b
M. P. oC (Lit.)
185-187
4
88
(180-182) [21]
2a
3
89
182-186
(185-187) [33]
3a
4a
5
3
90
92
205-207
(208-210) [19]
201-203
(200-202) [15]
5a
6a
3
5
91
87
203-205
(200-204) [19]
209-210
(208-210) [33]
7a
4
89
209-211
(209-210) [33]
123

Fabrication, identification and application of Fe3O4…
Table 3 continued
Entry
8a
Product
Time (min)
Yield (%)b
M. P. oC (Lit.)
4
91
180-182
(180-181) [33]
9a
8
7
84
83
202-203
(202-203) [33]
10a
180-183
(182-184) [22]
11a
12a
13
75
85
154-156
(152-154) [18]
7
211-213
(210-211) [33]
Reaction conditions: aldehydes (2 mmol), benzyl carbamate (2.2 mmol), 2-naphthol (2 mmol), Fe3-
O4@nicotinic acid @sulfonic acid chloride nanoparticles (0.02 g), solvent-free, 80 °C
aIsolated yield
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A. Khazaei et al.
R
OH
O
S
H
O
Fe OFe O
Fe O3
H
O
4
3
4
4
3
-H
2O
H
O
O
O
R
Cl
H
A
Ph
Ph
O
O
O
O
NH2
O
Fe3O4
H
O
S
R
NH
O
O
R
Cl
OH
B
Scheme 3 The plausible mechanism for the synthesis of 1-carbamato-alkyl-2-naphthols catalyzed by
Fe3O4@nicotinic acid @sulfonic acid chloride nanoparticles
Fig. 7 Reusability test of the Fe3O4@nicotinic acid @sulfonic acid chloride nanoparticles
123

Fabrication, identification and application of Fe3O4…
Fig. 8 FT-IR spectra: a fresh catalyst; b recovered catalyst
Acknowledgements We thank Bu-Ali Sina University and Iran National Science Foundation (INSF) for
financial support given to our research groups.
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