A magnetically recyclable iron oxide-supported copper oxide nanocatalyst (Fe3O4-CuO) for one-pot synthesis of: S -aryl dithiocarbamates under solvent-free conditions

Article abstract of DOI:10.1039/c5ra20524g

A green, convenient and efficient procedure is reported for the synthesis of S-aryl dithiocarbamates by a simple one-pot three component Ullmann-type condensation of an amine, carbon disulfide and an aryl iodide. Magnetically separable and reusable copper

Full text of DOI:10.1039/c5ra20524g

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A magnetically recyclable iron oxide-supported
copper oxide nanocatalyst (Fe3O4–CuO) for one-
pot synthesis of S-aryl dithiocarbamates under
solvent-free conditions
Cite this: RSC Adv., 2016, 6, 32018
F. Aryanasab
A green, convenient and efficient procedure is reported for the synthesis of S-aryl dithiocarbamates by
a simple one-pot three component Ullmann-type condensation of an amine, carbon disulfide and an
aryl iodide. Magnetically separable and reusable copper oxide (Fe3O4–CuO) nanoparticles are used as
a heterogeneous catalyst under base- and solvent-free conditions. Nanoparticles with an average size of
10–20 nm has been successfully prepared by a simple precipitation method in aqueous medium from
readily available inexpensive starting materials. The catalyst could be easily separated from the reaction
mixture by using an external magnet and recycled four times without significant loss in its activity.
Received 4th October 2015
Accepted 18th March 2016
DOI: 10.1039/c5ra20524g
www.rsc.org/advances
The main disadvantage of using neat metal and metal oxide
nanoparticles as catalyst is their poor recyclability and leaching
Introduction
effects nally leading to decreased yields. To overcome this
problem, copper and copper oxide supported catalysts and
nanocatalysts are employed in various organic reactions.
Selected recent examples include an impregnated copper on
magnetite in the synthesis of propargylamine42 and 1,3-diynes,43
iron oxide-supported copper oxide nanoparticles for the
synthesis of pyrazole derivatives, 4-methoxyaniline and
Ullmann-type condensation reactions44 and lepidocrocite sup-
ported copper oxide nanocatalyst (Fe–CuO) for the synthesis of
imidazole.45
Organic dithiocarbamates have received much attention
because of their interesting chemistry and wide range of utili-
ties. They have many potential applications as versatile
synthetic intermediates,46–52 linkers in solid phase organic
synthesis,53,54 protecting groups in peptide synthesis,55,56 agro-
chemicals,57–59 and biologically active compounds.60,61 They are
used in the rubber industry as vulcanization accelerators,62,63 in
medicinal chemistry64–67 and recently as single precursor sour-
ces for the preparation of nanoparticles.68–71 Conventional
methods for their synthesis involve reactions of amines with
toxic and expensive reagents, such as thiophosgene or an iso-
thiocyanate, which are not environmentally acceptable.72–74
Recently, several one-pot procedures reacting amines with
carbon disulde and alkyl/aryl halides, a,b-unsaturated
compounds or epoxides in water, in absence or presence of
metals have been developed to produce simple alkyl and aryl
dithiocarbamates.75–80 However, only a few methods are avail-
able to access S-aryl and S-vinyl dithiocarbamates. Some of the
procedures are involved with the Wittig reaction of aldehydes
with phosphonium ylides81 or reaction of the sodium salt of
Supported-heterogeneous catalysts have received great attention
in recent years and are an integral part of catalysis science and
technology. Due to the easy separation and purication process
of these catalytic systems, most important organic chemistry
industries rely on them.1–5 Consequently, it is important to design
unique supported-heterogeneous catalytic systems for organic
transformations; the most recent efforts being the synthesis of
metal or metal oxides supported catalysts or nanocatalysts.6–9
Several inorganic materials such as silica, carbon, alumina,
zirconia and iron oxides, as well as organic polymers, have been
used as a catalyst support for metal and metal oxide nano-
particles;10–16 among them, inexpensive iron oxides have gained
much attention due to their unique characteristics such as high
surface area and anchoring possibilities for immobilization of
active nanocatalysts. They have been well investigated as envi-
ronmentally benign catalysts or support in various important
organic transformations.17–23 Furthermore, their magnetic
response, as an alternative to ltration, provide an efficient
separation and recovery strategy and prevents loss of catalyst
and increases the reusability.24–26
Copper-catalyzed heteroatom cross-coupling reactions (C–N,
C–O and C–S) are very powerful tools in modern organic
synthesis. They provide a uniquely easy and convenient acces-
sibility to a wide range of structural variations.27–34 Particularly,
C–S bond forming reactions attracted signicant interest
because of the frequent occurrence of these structural units in
biologically active molecules.35–41
Department of Chemistry and Petrochemical Engineering, Standard Research Institute
(SRI), 31745-139 Karaj, Iran. E-mail: f_aryanasab@standard.ac.ir
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dithiocarbamic acid with hypervalent iodine compounds.82–84
Clearly, simple methods for the synthesis of S-aryl and S-vinyl
dithiocarbamates would be highly desirable. Recently, a new
protocol based on the Ullmann-type coupling of sodium
dithiocarbamates with aryl iodides and vinyl bromides cata-
lyzed by CuI in the presence of a ligand, N,N-dimethylglycine, in
DMF has been reported by Liu and Bao.85 Moreover, Ranu et al.
reported a one-pot three-component condensation of aryl/
styrenyl halides, carbon disulde, and amines using copper
nanoparticles for the synthesis of aryl and styrenyl dithiocar-
bamates in water.86 They also reported a catalyst-free procedure
for the synthesis of S-aryl dithiocarbamates using aryldiazo-
nium uoroborate in water at room temperature.87
In our previous work, we reported regioselective metal- and
solvent-free synthesis of S-vinyl dithiocarbamates.88 Herein,
a novel, convenient and efficient procedure is reported for the
one-pot synthesis of S-aryl dithiocarbamates by Ullmann-type
condensation of an amine, carbon disulde and an aryl
iodide using magnetically separable and reusable copper oxide
nanoparticles (Fe3O4–CuO MNPs) under base- and solvent-free
conditions.
Fig. 1 XRD patterns of (a) Fe3O4 MNPs and (b) Fe3O4–CuO MNPs.
The TEM image of Fe3O4–CuO (Fig. 2) shows uniform-sized
magnetic nanoparticles with somewhat spherical morphology.
The average size of Fe3O4–CuO was in the range of 10–20 nm.
Aer the successful preparation and characterization of
Fe3O4–CuO, its catalytic activity was examined for one-pot
synthesis of S-aryl dithiocarbamates. For optimization of the
reaction conditions, such as solvent, reaction time and reaction
temperature, the model reaction of phenyl iodide, pyrrolidine
and carbon disulde has been selected. The results are
summarized in Table 1.
Results and discussion
The Fe3O4–CuO MNPs were prepared following the literature44,89
(Scheme 1). The structure of nanocatalyst was established
previously,11,44,89 in present work it was also characterized by X-
ray diffraction (XRD), inductive coupled plasma optical emis-
sion spectroscopy (ICP-OES) and transmission electron
microscopy (TEM).
It should be noted that no product formation was observed
in the absence of Fe3O4–CuO nanoparticles at room tempera-
ture. The same reaction was repeated at 130 ꢀC, and only a trace
amount of coupling product was formed (Table 1, entry 16). The
reaction yield when catalytic amount of Fe3O4–CuO MNPs were
Based on the ICP-OES analysis, the weight percentage of Cu
was determined to be 4.50%. The phase structure and crystal-
linity of Fe3O4 and Fe3O4–CuO nanoparticles were investigated
by XRD, and the results are given in Fig. 1. For the XRD pattern
of Fe3O4 nanoparticles (curve a), the diffraction peaks at 2q ¼
29.4ꢀ, 35.8ꢀ, 44.7ꢀ, 54.8ꢀ, 58.8ꢀ, 65.7ꢀ matched well with the
(220), (311), (400), (422), (511), (440) planes of Fe3O4 (JCPDS 79-
0419). Besides typical peaks of Fe3O4, four new peaks with 2q
values of 31.8ꢀ, 39.4ꢀ, 51.5ꢀ and 61.1ꢀ were identied in the XRD
pattern of Fe3O4–CuO (curve b), and they were indexed for the
crystal faces of (110), (111), (020), (311) of monoclinic phase of
CuO crystals (JCPDS 048-1548). The crystallite size of Fe3O4
nanoparticles, calculated using the Debye–Scherrer equation,
from the 2q ¼ 35.8ꢀ peak, was found to be 13 nm and the
crystallite size of CuO nanoparticles, from the 2q ¼ 39.4ꢀ peak,
was found to be 17 nm.
ꢀ
added in solvent-free condition at 90 C, aer 10 h, was 70%
ꢀ
(Table 1, entry 10), while at 130 C aer 8 h the yield was 96%
(Table 1, entry 11). Bases such as K2CO3 and KOH are found to
have no signicant effect in the yield of the reactions (Table 1,
entries 1–8). The results showed that 130 ꢀC was required for the
coupling reaction to give 96% yield of the product (Table 1,
entry 11). Shorter or longer reaction time than 8 h and lower or
higher temperature than 130 ꢀC decelerated the reaction rate
Fig. 2 TEM image of Fe3O4–CuO MNPs showing particle size distri-
Scheme 1 Synthesis of Fe3O4–CuO nanocatalyst.
bution: the corresponding histogram is superimposed onto image.
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Table 1 Optimization of the reaction conditions for coupling reaction of phenyl iodide with dithiocarbamate anion
Entry
Catalyst
Solvent
Base
Time (h)
Temp (ꢀC)
Yielda,b (%)
1
2
3
4
5
6
7
8
Fe3O4–CuO
Fe3O4–CuO
Fe3O4–CuO
Fe3O4–CuO
Fe3O4–CuO
Fe3O4–CuO
Fe3O4–CuO
Fe3O4–CuO
Fe3O4–CuO
Fe3O4–CuO
Fe3O4–CuO
Fe3O4–CuO
Fe3O4–CuO
Fe3O4–CuO
Fe3O4–CuO
—
DMF
DMSO
Toluene
H2O
DMF
DMSO
Toluene
H2O
—
—
—
—
—
K2CO3
K2CO3
K2CO3
K2CO3
KOH
KOH
KOH
KOH
—
—
—
—
—
8
5
10
10
8
70
80
80
90
70
80
80
90
90
60
65
57
40
50
58
45
35
60
70
96
90
96
80
70
Trace
85
5
10
10
5
10
8
8
10
5
9
10
11
12
13
14
15
16
17
90
130
150
130
130
130
130
130
—
—
—
—
—
—
—
—
3
8
8
CuFe2O4
a
Isolated yield. b Reaction condition: catalyst (20 mg), phenyl iodide (1 mmol), pyrrolidine (1.2 mmol), CS2 (3 mmol), base (1.5 mmol) in 3 mL of
solvent. NR ¼ no reaction.
and led to lower product yields (Table 1, entries 9–15).
Commercial available CuFe2O4 also used as catalyst in the investigated by recycling experiments for the reaction between
model reaction and gave lower yield (Table 1, entry 17). pyrrolidine, CS2 and phenyl iodide under the optimized condi-
The stability of Fe3O4–CuO nanocatalyst and its activity were
With optimized reaction conditions in hand, other S-aryl tions reported in Table 1 (entry 11). Aer each cycle, the catalyst
dithiocarbamates were prepared by the coupling reaction of was separated by an external magnet, washed with ethanol,
several substituted aryl iodides with dithiocarbamate anions, dried at 60 ꢀC in a vacuum oven to remove residual solvents, and
generated in situ by the reaction of carbon disulde and amines used for the next cycle. It was found that Fe3O4–CuO nano-
(Scheme 2). The results are summarized in Table 2. A variety of particles could be recycled four times without signicant loss of
electron-donating and electron-withdrawing substituents in the its initial catalytic activity. The reusability test has been shown in
aromatic ring, such as OMe, CH3, Cl and COMe, are compatible in Table 3.
this reaction. Unfortunately, bromobenzene gave only trace
In order to prove that the Fe3O4–CuO nanocatalyst is
amounts of desired product under the conditions described (Table heterogeneous, a standard leaching experiment was conducted
2, entry 17). Ranu et al., used Cu nanoparticles as a catalyst for the by the hot ltration method. The coupling reaction of phenyl
synthesis of S-aryl dithiocarbamates with the similar substrates.86 iodide, pyrrolidine and carbon disulde proceeded for 30 min
ꢀ
But the present catalytic system is separable and can be recycled in the presence of Fe3O4–CuO nanocatalyst at 130 C, then the
and used four times without signicant loss in its catalytic activity. catalyst was removed using an external magnet. It was observed
The present procedure provides a one-pot approach and avoids the that the reaction did not reach completion even aer 24 h. This
use of sodium salt of dithiocarbamic acid that Bao et al., used for clearly conrmed that no homogeneous catalyst was involved.
the synthesis of S-aryl dithiocarbamates.85 In addition, present ICP-OES analysis of the ltrate (hot) was also done to determine
protocol did not require a base or a ligand and avoids the use of the leaching of metal in the reaction mixture and revealed the
toxic organic solvents by performing solvent-free conditions.
absence of Fe and Cu species in the ltrate.
Experimental section
Materials and reagents
The reagents such as FeCl3$6H2O, FeCl2$4H2O, CuCl2$2H2O,
phenyl iodide, CS2 and amines were purchased from Sigma-
Aldrich and Merck and were used as received without any
further purication.
Scheme 2 Coupling reaction of various aryl iodides with dithiocar-
bamates catalyzed by Fe3O4–CuO MNPs.
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Table 2 Fe3O4–CuO MNPs. Catalyzed coupling of aryl iodides with dithiocarbamates
Entry
1
Aryl halide
Amine
Time (h)
8
Product
Yielda,b (%)
96
Ref.
86 and 87
2
3
8
90
80
85–87
10
86, 87 and 90
4
5
6
8
10
10
95
80
78
82, 86, 87 and 91
86 and 87
82 and 87
7
12
12
10
12
65
78
75
68
87
8
87 and 91
82 and 87
87
9
10
11
12
13
14
15
10
8
80
80
78
70
74
82 and 87
86
87
87
82
8
9
10
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Table 2 (Contd.)
Entry
16
Aryl halide
Amine
Time (h)
12
Product
Yielda,b (%)
Ref.
65
87
17
18
Trace
a
All the reactions were performed with Fe3O4–CuO MNPs (20 mg), aryl iodide (1 mmol), amine (1.2 mmol), CS2 (3 mmol). b Isolated yield.
quickly in the external magnetic eld. The obtained black
Measurements
powder (Fe3O4 MNPs) was washed, and dried in vacuum oven.
1
The H NMR spectra were recorded at 300 MHz, and 13C NMR
spectra were recorded at 75 MHz in CDCl3 using TMS as an
internal standard. Thin layer chromatography (TLC) was carried
out on Merck 60 GF 254 plates coated with a 0.2 mm layer of
silica gel. The spots were visualized using UV 254 light. The
Fourier transformation infrared (FT-IR) spectra were recorded
(Shimadzu, Japan) as KBr pellets in the wavenumber range
4000–400 cmꢁ1. Transmission electron microscopy (TEM)
images were obtained on an EM10C (Zeiss) transmission elec-
tron microscope at an accelerating voltage of 80 kV. Powder
X-ray diffraction (XRD) measurements were collected using
Preparation of Fe3O4–CuO nanocatalyst
Magnetite nanoparticles, Fe3O4, (2 g) was added to a solution of
copper chloride dihydrate (CuCl2$2H2O, for 5 wt% of Cu on
magnetite) in H2O (50 mL) and mechanically stirred at room
temperature for 1 h. Aer impregnation, the suspension was
adjusted to pH 12–13 by adding sodium hydroxide (1.0 M) and
further stirred for 20 h. The solid was washed with distilled
water (5 ꢂ 10 mL), and the resulting Fe3O4–CuO nanoparticles
were sonicated for 10 min, washed with distilled water and
subsequently with ethanol, and dried in a vacuum oven at 60 ꢀC
for 24 h. The Cu content of Fe3O4–CuO nanoparticles was found
to be 4.50% as determined by ICP-OES.
˚
Philips PW3710 diffractometer (Co Ka radiation (l ¼ 1.78 A)).
Copper elemental analysis was determined with an inductively
coupled plasma optical emission spectrometry (ICP-OES)
(Thermo Scientic, IRIS Intrepid II, USA) coupled to a pneu-
matic nebulizer and equipped with a charge coupled device
(CCD).
Synthesis of S-aryl dithiocarbamates
Representative experimental procedure for the condensation
of pyrrolidine, CS2 and phenyl iodide (Table 1, entry1). In
a 50 mL round-bottom ask, tted with a magnetic stir-bar in an
ice-bath, CS2 (3 mmol) was added to pyrrolidine (1.2 mmol) and
stirred for 10 min. Then, Fe3O4–CuO MNPs (20 mg) and phenyl
iodide (1 mmol) was added. The reaction mixture was then
Preparation of Fe3O4 MNPs
5.94 g ferric chloride hexahydrate was dissolved in 200 mL
highly puried water within a three neck ask. Under a nitrogen
atmosphere, 2.20
g
ferrous chloride tetrahydrate was
ꢀ
added with vigorous mechanical stirring at 85 C. Then 10 mL
30% (v/v) NH3$H2O was added with further increased stirring
speeds, and the orange-red clear solution became a black
suspension immediately. The molar ratio of Fe(III) to Fe(II) in the
above system was nearly 2.00. The reaction was stopped aer
half an hour, and the obtained suspension was cooled down to
room temperature. The magnetic nanoparticles were sequen-
tially washed with deionized water, 0.02 mol Lꢁ1 sodium chlo-
ride and ethanol for several times until solution was claried
ꢀ
heated at 130 C. The progress of the reaction was monitored
with thin-layer chromatography (TLC). Aer completion of the
reaction (8 h), the reaction mixture was cooled to room
temperature, then water (15 mL) was added and the magnetic
nanocatalyst was separated from the mixture using an
external magnet. The product was extracted with ethyl acetate
(3 ꢂ 10 mL). Evaporation of the solvent gave a crude product
that puried by simple crystallization from ethanol to provide
the corresponding S-aryl dithiocarbamate, pyrrolidine-1-
carbodithioic acid phenyl ester, as a pale yellow solid, mp
97–99 ꢀC, FT-IR (KBr) 2935, 2842, 1565, 1461, 1269, 1120, 1005,
970, 854, 740, 674 cmꢁ1; 1H-NMR (300 MHz, CDCl3) d 1.97–2.06
(m, 2H), 2.10–2.19 (m, 2H), 3.81 (br, 2H), 3.95 (br, 2H), 7.41–7.53
(m, 5H) ppm; 13C-NMR (75 MHz, CDCl3) d 24.3, 26.2, 51.0, 55.3,
129.0 (2C), 130.0, 130.9, 136.8 (2C), 203.0 ppm.
Table 3 Reusability study of Fe3O4–CuO nanocatalyst
Entry
Yielda, %
1
2
3
4
96
94
90
88
The compounds synthesized by above procedure are listed in
Table 2. All of the products are known, and the structure of the
products were determined from their NMR spectra and by
comparison with those reported in the literature.
a
Isolated yield aer each run.
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In summary, a magnetically recyclable and highly efficient
Fe3O4–CuO nanocatalyst was designed and synthesized. The
catalyst used for a mild and efficient preparation of S-aryl
dithiocarbamates under Ullmann-type coupling reaction in
solvent-free conditions without using any base or ligand.
Various S-aryl dithiocarbamates were synthesized in good yield
under benign reaction conditions. This catalyst was found to be
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