Expeditious one-pot three component synthesis of N-aryl dithiocarbamate derivatives using mesoporous Cu-materials

Article abstract of DOI:10.1016/j.tetlet.2015.01.158

In this study, a facile one-pot three component protocol has been demonstrated for the preparation of synthetically challenging N-aryl dithiocarbamate derivatives using mesoporous Cu-materials as catalyst at room temperature. The mesoporous Cu-catalysts namely Cu-MCM-41, Cu-MCM-48, and Cu-SBA-15 were prepared by impregnation of Cu-salts on the synthesized mesoporous materials and were characterized by powder X-ray diffraction, N₂ adsorption-desorption, and transmission electron microscopic studies. Significant improvement of yields was obtained using mesoporous Cu-catalysts under milder reaction conditions compared to the earlier reported catalysts. All the three mesoporous Cu-catalysts showed comparative reactivity however a little higher yield was obtained using Cu-MCM-48.

Full text of DOI:10.1016/j.tetlet.2015.01.158

Accepted Manuscript
Expeditious one-pot three component synthesis of N-aryl dithiocarbamate de-
rivatives using mesoporous Cu-materials
Soumen Payra, Arijit Saha, Rui Peng, Chia-Ming Wu, Ranjit T. Koodali,
Subhash Banerjee
PII:
S0040-4039(15)00208-7
DOI:
http://dx.doi.org/10.1016/j.tetlet.2015.01.158
TETL 45828
Reference:
Tetrahedron Letters
To appear in:
Received Date:
Revised Date:
Accepted Date:
11 December 2014
23 January 2015
24 January 2015
Please cite this article as: Payra, S., Saha, A., Peng, R., Wu, C-M., Koodali, R.T., Banerjee, S., Expeditious one-pot
three component synthesis of N-aryl dithiocarbamate derivatives using mesoporous Cu-materials, Tetrahedron
Letters (2015), doi: http://dx.doi.org/10.1016/j.tetlet.2015.01.158
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Expeditious one-pot three component
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Leave this area blank for abstract info.
Soumen Payra, Arijit Saha, Rui Peng, Chia-Ming Wu, Ranjit T. Koodali*
and Subhash Banerjee*
NH2
W
S
R
CS2
W
N
H
S
Mesoporous Cu-materials

1
Tetrahedron Letters
journal homepage: www.els evier.com
Expeditious one-pot three component synthesis of N-aryl dithiocarbamate
derivatives using mesoporous Cu-materials
Soumen Payraa Arijit Sahaa Rui Pengb Chia-Ming Wub, Ranjit T. Koodalib,* and Subhash Banerjeea,*
a Department of Chemistry, Guru Ghasidas Vishwavidyalaya (a Central University), Bilaspur-495009, Chhattisgarh, India.
bDepartment of Chemistry, The University of South Dakota, 414 E. Clark Street, Vermillion, SD, 57069, USA.
*Corresponding authors, Email: ocsb2009@yahoo.com (S.B.); ranjit.koodali@usd.edu (R.T.K.)
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
In this study, a facile one-pot three component protocol has been demonstrated for the
preparation of synthetically challenging N-aryl dithiocarbamate derivatives using mesoporous
Cu-materials as catalyst at room temperature. The mesoporous Cu-catalysts namely Cu-MCM-
41, Cu-MCM-48, and Cu-SBA-15 were prepared by impregnation of Cu-salts on the synthesized
mesoporous materials and were characterized by powder X-ray diffraction, N2 adsorption-
desorption, and transmission electron microscopic studies. Significant improvement of yields
was obtained using mesoporous Cu-catalysts under milder reaction conditions compared to the
earlier reported catalysts. All the three mesoporous Cu-catalysts showed comparative reactivity
however a little higher yield was obtained using Cu-MCM-48.
Available online
Keywords:
Mesoporous Cu-materials
N-aryl dithiocarbamate derivatives
Multicomponent reactions
C-N and C-S bond formation
2009 Elsevier Ltd. All rights reserved.
o
CuI/N,N-dimethylglycine/K2CO3 in DMF at 110 C. However,
Synthesis of dithiocarbamates is important as they are
valuable synthetic intermediates1 and found in bio-active
compounds.2 Functionalized carbamates specially diarylalkyl
thioureas are known to exhibit interesting medicinal and
biological properties2 and are used as non-vanilloid TRPV1
antagonists, possessing excellent therapeutic potentials in pain
regulation3 and human CB1 and CB2 cannabinoid receptor
affinity.4 For these reasons, the synthesis of dithiocarbamate
derivatives with different substitution patterns at the thiol chain
has become a field of increasing interest in synthetic organic
chemistry during the past few years.
longer reaction time (22 h), high temperature, and use of
nitrogenous ligand are the major limitations of the protocol.10 On
the other hand, N-aryl dithiocarbamate derivatives have been
11a
synthesized by using SnCl2 and basic Al2O3 as catalyst.11b
However, these methods required longer time (10-30 h),
produced low isolated yields of products, and often made use of
toxic reagents (e.g. SnCl2), harsh organic solvents such as DMF,
DMSO and methanol 10,11 making these reactions laborious, time-
intensive, and inefficient.
Thus, development of efficient and environment-friendly
heterogeneous catalyst for the synthesis of biologically important
N-aryl substituted dithiocarbamate derivatives is in great demand.
However, heterogenization of homogeneous catalysts
considerably decreases their catalytic efficiency by blocking the
active sites of the catalysts. Thus, design and development of
porous supports is essential for heterogenization of homogeneous
catalysts. In this context, the development of mesoporous silica
materials designated as M41S12 by Mobil Oil Corporation in
1992 enables one to tune the catalytic activity and selectivity of
heterogeneous catalyst by changing their surface area and pore
size. The pores in M41S class materials are uniform and are
aligned in hexagonal (MCM-41), cubic (MCM-48) and lamellar
(MCM-50) structures. The large surface area and narrow pore
size distributions (tunable from 2 to 10 nm) make them an ideal
support for catalytic reactions. Among the M41S class of
materials, MCM-48 is interesting candidate as they possess
relatively high surface areas (> 1000 m2g-1) which enables high
dispersion of active sites of catalyst, good thermal stability, and
finally, the interpenetrating network of three-dimensional pores,
facilitate molecular transport of reactants and products more
Several methods for the synthesis of dithiocarbamate
derivatives have been reported in the literature, and among them,
reactions of amines with costly and toxic reagents, such as
thiophosgene and isothiocyanate, have been reported as the
general routes.5 Direct thiocarboxylation of amines with carbon
monoxide and sulfur to form urea derivatives has been reported. 6
Recently, a one-pot reaction of amines with carbonyl sulfide,
alkyl halides, or α,β-unsaturated compounds also has been
developed.7 However, most of the above described methods have
focused on the synthesis of alkyl dithiocarbamates and limited
methods are present in the literature for the synthesis of aryl
dithiocarbamates. Generally, these moieties have been prepared
by the reactions sodium salt of dithiocarbamic acid,8 or certain
organometallic reagents with tetramethylthiuram disulfide.9
S-aryl-N-alkyl dithiocarbamate derivatives have been prepared
by Bao et al.10 via Ullmann-type coupling reaction of sodium
dithiocarbamates with aryl iodides and vinyl bromides using

2
Tetrahedron
efficiently compared to one-dimensional supports such as MCM-
41.13 On the other hand, SBA-15 an another well-known
mesoporous silica sieve having uniform hexagonal pores with a
narrow pore size distribution and larger pore diameter, which is
also expected to enhance catalytic performance by assisting mass
transport of reactant(s) and product(s).14 Various transition
metals in the form of metal or metal oxide have been
incorporated into the framework positions in these mesoporous
materials and/or have been dispersed onto the surface of siliceous
mesoporous materials.15 The idea behind this present work is that
by dispersing catalytically active copper species on a high surface
area mesoporous support with relatively large, uniform, and
regular pores, one can realize high catalytic activity for the
preparation of synthetically challenged N-aryl dithiocarbamate
derivatives.
is indicated by the characteristic peaks at the (100), (110), and
(200) reflections consistent with SBA-15 mesostructure.20
Therefore, the loading of Cu does not destroy the periodic
mesoporous structure of the MCM-41, MCM-48, or SBA-15
support. The high-angle powder XRD experiments of the Cu-
based mesoporous materials were also investigated and the
results (not shown) indicate the presence of a very broad peak at
2θ near 25o which is due to the presence of the amorphous silica
support. No other peaks were observed indicating that the copper
species is highly dispersed on the high surface area support
precluding its detection. Alternatively, it is also possible that the
copper moieties are also in the amorphous form and hence are not
detected. Thus, the powder XRD measurements indicate that the
mesostructure is preserved on loading with Cu-species and that
they are well dispersed on the mesoporous support.
In this paper, we demonstrate the facile one-pot three
component fabrication of synthetically challenging N-aryl
substituted dithiocarbamate derivatives using mesoporous
supported Cu-catalysts at room temperature in ethanol. Briefly,
mesoporous, Cu-MCM-41, Cu-MCM-48 and Cu-SBA-15 have
been prepared by impregnation of Cu-salt on mesoporous
materials and well-characterized by powder X-ray diffraction
(XRD) and N2 adsorption-desorption isotherms and transmission
electron microscopic (TEM) studies and finally comparative
studies have been performed for the synthesis of N-aryl-
dithiocarbamate derivatives (Scheme 1).
Next, we have studied the N2 adsorption-desorption of
materials to determine the physicochemical properties. The N2
adsorption-desorption isotherms of the catalysts were performed
using a Quantachrome Nova 2200e gas adsorption analyzer at
77K. Samples were dried in an air oven overnight and degassed
at 100 oC extensively, prior to the adsorption measurements. The
nitrogen adsorption/desorption isotherms of mesoporous Cu-
MCM-41, Cu-MCM-48, and Cu-SBA-15 were given in the
supporting information. The surface area was determined using
the Brunauer–Emmett–Teller (BET) equation in the relative
pressure range of (P/P0) = 0.05 to 0.30. The pore sizes were
calculated by applying the Barrett-Joyner-Halenda (BJH)
equation to the desorption isotherm. The pore volume was
calculated from the amount of nitrogen adsorbed at the highest
C-S bond formation
NH2
Mesoporous
Cu-catalyst
R
W
S
R
CS2
W
relative
pressure
(P/P0)
~
0.98.
The
nitrogen
Room temp.
N
H
S
adsorption/desorption isotherms the pore size distribution plots of
the various Cu-based mesoporous catalysts were given in the
supporting information (see Figure S2 and S3 in SI-2). Table 1
lists the surface area (SBET), pore diameter (Dp) and total pore
volume (Dv) of mesoporous Cu-catalysts.
C-N bond formation
Scheme 1. Synthesis of N-aryl-dithiocarbamate derivatives using
Cu supported mesoporous materials.
As listed in Table 1, Cu-MCM-41, Cu-MCM-48 and Cu-SBA-
15 materials have surface areas of 954, 565, and 493 m2g-1
respectively. A steady increase in surface area was observed from
SBA-15 to MCM-41.
Initially, we have synthesized Cu-MCM-41, Cu-MCM-48 and
Cu-SBA-15 by simple impregnation of Cu-salt onto the surface
of pre-synthesized mesoporous silica materials followed by
calcination following reported procedure.16-18 The detailed
experimental procedure for the preparation of Cu-MCM-41, Cu-
MCM-48 and Cu-SBA-15 are given in the supporting
information. The structural and physico-chemical properties of
the three materials were determined by powder XRD, N2
adsorption-desorption and transmission electron microscopic
(TEM) studies.
Table 1. Physicochemical properties of Cu-MCM-41, Cu-MCM-
48 and Cu-SBA-15
Entry
Cu-catalyst
SBET
Dv
Dp
(m2/g)
(cm3/g) (nm)
1
2
3
Cu-MCM-41
Cu-MCM-48
Cu-SBA-15
954
565
493
0.49
0.31
0.74
2.2
1.9
6.6
The powder X-ray diffraction patterns (XRD) of the Cu-based
mesoporous catalysts were recorded on a Rigaku Ultima IV X-
ray diffractometer using Cu Kα radiation of λ= 1.540806 Å. The
diffractometer was operated at 40 kV and 40 mA and with a step
width of 0.02° and the scan rate used was 0.24°/min.
These materials have pore volumes (Dv) of 0.49, 0.31 and 0.74
cm3/g respectively whereas the pore diameters (Dp) were
determined to be 2.2, 1.9, and 6.6 nm respectively. Thus, Cu-
SBA-15 contains larger pore volumes and pore diameter (Table
1, entry 3).
The powder XRD studies (see Figure S1 in the supporting
information) revealed that Cu-MCM-41 has diffraction peaks at
2θ = 2.3°, and 4.5° due to (100) and (110) reflection planes
respectively and the powder XRD pattern is consistent with
MCM-41 type of materials.16 The powder XRD pattern of Cu-
MCM-48 is also similar to cubic MCM-48 reported by us
previously17 with the basal diffraction peaks at 2θ = 2.7° and
3.1°, corresponding to (211) and (220) diffractions of the Ia d
cubic structure.19 The powder diffraction pattern of Cu-SBA-15
Transmission electron spectroscopy (TEM) images were
obtained using an FEI Tecnai G2 Spirit instrument at an
acceleration voltage of 120 kV. TEM images were recorded by
first sonicating a dispersion consisting of the mesoporous sample
in ethanol and then by carefully placing a drop of the sonicated
dispersion on a carbon-coated copper grid (mesh size = 200).

3
This was allowed to air dry overnight before transferring to the
vacuum chamber of the TEM instrument. The transmission
electron micrograph of a representative Cu-based mesoporous
material (Cu-SBA-15) is shown in Figure 1. The well-ordered
cylindrical pore geometry of the mesoporous SBA-15 support
can be seen in the TEM image (Figure 1). The TEM images
corresponding to Cu-MCM-41 and Cu-MCM-48 are given in the
supporting information (see figure S4 and S5).
highest reactivity in ethanol showing 95% yield of the product.
Assuming that all the Cu moieties are active sites, the turnover
rate for the conversion of aryl aniline as indicted in Table 2 for
Cu-MCM-41, Cu-MCM-48, and Cu-SBA-15 is calculated to be
1.98 x 103 h-1, 2.35 x 103 h-1, and 2.10 x 103 h-1 respectively
indicating that the reactions are catalytic in nature. The reaction
in EtOH-H2O (1:1) mixture also yielded impressive yields (90%).
20 mg of Cu-MCM-48 was sufficient for this conversion and
increasing amount of catalyst did not increase the yield of the
product.
Table 3. Solvents effect of on Cu-MCM-48 catalyzed synthesis
of methyl 3-((phenylcarbamothioyl)thio)propanoate.
S
Cu-MCM-48
+
Ph-NH2 CS2
+
CO2Me
CO2Me
PhHN
S
Solvent
Entry Cu-MCM-48 Solvent
Time
Yielda
(min.)
%)
75
95
80
90
1
2
3
4
Cu-MCM-48 CH3CN
Cu-MCM-48 EtOH
Cu-MCM-48 H2O
60
60
60
Cu-MCM-48 EtOH:H2O 60
(1:1)
5
6
Cu-MCM-48 THF
60
60
35
96
Figure 1. Transmission electron microscope image of
mesoporous Cu-SBA-15.
Cu-MCM-
48b
EtOH
The catalytic activity of the mesoporous Cu-materials were
tested for the synthesis of aryldithiocarbamate derivatives and a
three component reaction of aniline, CS2, and methyl acrylate has
been chosen as a model reaction. When methyl acrylate (1.1
mmol) was added to a stirred solution of aniline (1 mmol), CS2
(2.5 mmol) and Cu-materials (20 mg) in ethanol, excellent yields
of products was observed. As reflected in Table 2, all three Cu-
catalysts produced good to excellent yields of products.
However, Cu-MCM-48 provided a slightly higher yield of N-
phenyl dithiocarbamate. The higher reactivity of Cu-MCM-48 is
probably due to the three-dimensional interpenetrating network
of pores in the cubic material that facilities enhanced molecular
trafficking of reactants and products in comparison to the uni-
dimensional nature of pores in MCM-41 and SBA-15 that is
more prone to clogging effects. The non-doped catalyst, MCM-
48 exhibited little activity and yielded 22 % of product after 12
hours stirring at room temperature (entry 4, Table 2).
Reaction Conditions: Aniline (1 mmol), CS2(2.5 mmol),
methyl acrylate (1 mmol), Solvent (2 ml), 10% Cu-MCM-
b
48 (20 mg), Stirring at room temparature. a Isolated yield,
50 mg of 10% Cu-MCM-48 was used.
Using the optimized reaction conditions i.e. 20 mg of Cu-MCM-
48 in ethanol at room temperature we have explored the scope for
the synthesis of different N-aryl-S-substituted dithiocarbamate
derivatives. In a simple experimental procedure,21 aromatic
amines (1 mmol) were treated with CS2 (2.5 mmol) in presence
of Cu-MCM-48 (20 mg) in ethanol (1 ml) and stirred for 20
minutes at room temperature. After that different conjugated
alkenes were added and stirred till completion of reaction
(monitored by thin layer chromatography). The solid products
were dissolved in hot ethanol and the catalyst was filtered,
washed with ethanol, dried, and reused for subsequent reactions.
The filtrate was kept at room temperature and crystals of
dithiocarbamate derivatives appeared. The crystals were
separated by filtration and washed with ethanol (2 x 1 ml) and
dried in oven at 50 oC. The formation of products was confirmed
by melting point determination and spectroscopic analysis. The
melting points were in well-accordance with reported values and
spectral data were also in good agreement with reported values in
literature. The results for the mesoporous Cu-MCM-48 catalyzed
synthesis of N-aryl dithiocarbamates have been presented in
Table 4. It was observed that aniline and 4-methoxyaniline
(containing an electron donating substituent) participated in three
component reactions without any difficulty however; presence of
a electron withdrawing substituent on the aniline aromatic ring
(e.g. 4-nitroaniline) retarded the reactions resulting in lower
yields of the products (entry 7, Table 4). This is due to the fact
that lone pair of electron on nitrogen in case of 4-nitroaniline
delocalized to nitro group (-R effect) via resonance and decreases
the rate of reaction. On the other hand, electron donating nature
of -OMe group (+R effect) accelerate the rate of reaction by
increasing the electron density on nitrogen. The presence of
Table 2. Study of catalytic activity of mesoporous Cu-materials
NH2
CO2Me
S
Cu-catalyst
Solvent
CS2
CO2Me
N
H
S
Yield
(%)a
Entry
Catalyst
Solvent
Time
(h)
1
2
3
4
Cu-MCM-41
Cu-MCM-48
Cu-SBA-15
MCM-48
EtOH
EtOH
EtOH
EtOH
1
1
80
95
85
22
1
12
a Yields refer to those of pure isolated products.
Next, we have examined the effect of solvents in this reaction
using Cu-MCM-48 catalyst and found that the catalysts showed

4
Tetrahedron
methyl group at ortho position of aromatic amine dose not retards
the rate of the reaction (entry 9, Table 4). However, when the
same reaction was conducted with 2,6-dimethyl aniline, a
significant decrease in yield was observed and only 65% product
was obtained (entry 8, Table 4) In addition, the reaction using
diphenyl amine was not successful and starting material was
recovered even after 2 h stirring at room temperature. The slower
rate with 2,6-dimethyl aniline and non-reactivity of diphenyl
amine could be possibly due the steric hindrance at the reaction
center. The reactions provide high yields within one hour.
Table 5. Comparative results of catalysts for the synthesis of N-
aryl dithiocarbamate derivatives via one-pot three component
reaction of aryl amine, CS2 and conjugated alkenes
Entry
Catalysts/Conditions
Time
(h)
Yield
(%)
Ref.
1
CuI/N,N-
22
75-95
10
dimethylglycine/K2CO3
in DMF/100 oC
2
3
4
SnCl2
2.5
89-95
30-93
11a
11b
Table 4. Synthesis of N-aryl dithiocarbamate derivatives using
Cu-MCM-48.
Basic Al2O3
10-30
Mesoporous
Cu-materials
0.5-1.5 65-96
Present
work
Entry Ar-NH2
1
Time
(min.) (%)
Yielda
W
OMe
60
95
The results in Table 5 clearly demonstrated the advantages of the
present synthetic route using mesoporous Cu-materials in terms
of the following criteria: (i) mild and neutral reaction conditions
(room temperature), (ii) faster reaction (1.5 h) compared to
reported methods11 and (iii) high isolated yields of the products.
With the advantageous just listed, the protocol using mesoporous
Cu-materials fulfills the criteria for green synthesis.
NH2
NH2
NH2
O
O
O
O
2
3
OBu
NH2
55
96
55
40
95
94
OMe
4
Conclusion
MeO
NH2
NH2
NH2
NH2
In conclusion, mesoporous supported Cu-catalysts namely Cu-
MCM-41, Cu-MCM-48, and Cu-SBA-15 have been prepared by
simple impregnation of Cu-salt to synthesized mesoporous
materials and characterized by powder XRD, nitrogen
adsorption-desorption, and TEM studies. The mesoporous
supported Cu-catalysts have showed excellent catalytic
performance for the construction of synthetically challenged and
biologically important N-aryldithiocarbamate derivatives at room
temperature under mild conditions. All three catalysts produced
good to excellent yields of N-aryldithiocarbamate derivatives at
room temperature and higher yield was obtained using Cu-MCM-
48 catalyst. The higher reactivity for Cu-MCM-48 is probably
due to the interpenetrating network of three-dimensional pores in
the cubic material that facilities enhanced diffusion of reactants
and products in comparison to the one-dimensional nature of
pores in MCM-41 and SBA-15 that is more prone to clogging
effects. The present protocol offers several advantages such as
mild reaction conditions (room temperature), faster reaction (1
h), easy separation of catalyst from the reaction mixture, high
isolated yields of the products (up to 95%) and environment-
friendly in nature.
5
OBu
NH2
40
30
90
90
92
95
65
65
MeO
O
O
O
O
6
MeO
OMe
OMe
7
O2N
8
9
NH2
OMe
45
80
NH2
O
Reaction Conditions: Aniline derivative (1 mmol), Carbon
disulfide (2.5 mmol), Conjugated alkene (1 mmol), EtOH (2
ml), Cu-MCM-48 (20 mg), Stirring at room temperature
aIsolated yield.
Acknowledgments
The funding agencies, Department of Science and Technology,
New Delhi, Govt. of India (No. SB/FT/CS 023/2012); University
Grant Commission, New Delhi, Govt. of India (No. F. 20-
1/2012(BSR)/20-8(3)2012(BSR) are greatly acknowledged. We
are also thankful to NSF–CHE–0722632, NSF–EPS–0903804,
and SD NASA-EPSCOR NNX12AB17G for financial support.
This present protocol for the synthesis of N-aryl substituted
dithiocarbamates has several advantages over previously reported
methods and a comparative result of catalytic performance of
mesoporous Cu-materials with the reported catalysts for the
synthesis of N-aryl dithiocarbamate derivatives has been
presented in Table 5. The results in Table 5 clearly demonstrated
the advantages of the present synthetic route using mesoporous
Cu-materials in terms of the following criteria: (i) mild and
neutral reaction conditions (room temperature), (ii) faster
reaction (1.5 h) compared to reported methods11 and (iii) high
isolated yields of the products.
Supplementary Material
Experimental procedure for the preparation of Cu-MCM-41, Cu-
MCM-48 and Cu-SBA-15 materials, characterization data of Cu-
Mesoporous materials such as Small-angle X-ray diffraction
patterns of Cu-MCM-41, Cu-MCM-48, and Cu-SBA-15
materials, nitrogen adsorption/desorption isotherms of

5
11. (a) Nagarapu, L.; Bantu, R.; Puttireddy, R. Applied Catalysis A:
mesoporous Cu-MCM-41, Cu-MCM-48, and Cu-SBA-15, pore
size distribution of Cu-MCM-41, Cu-MCM-48, and Cu-SBA-15,
TEM images of Cu-MCM-41, Cu-MCM-48 and copies of 1H
NMR spectra of N-aryl dithiocarbamate derivatives are available
free of charge at www.sciencedirect.com.
General, 2007, 332, 304-309; (b) Xia, S.; Wang, X.; Ge, Z.-M.;
Cheng, T.-M.; Li, R.-T.; Tetrahedron, 2009, 65, 1005-1009.
12. (a) Kresge, C.T.; Leonowicz, M. E.; Roth, W. J.; Vartuli, J. C.;
Beck, J. S. Nature, 1992, 359, 710-712; (b) Beck, J.S.; Vartuli,
J.C.; Roth, W.J. J. Am. Chem. Soc. 1992, 114, 10834-10843.
13. Fraile,J. M.; Garcia, J. I.; Mayoral, J. A.; Vispe, E.; Brown, D. R.;
Naderi, M. Chem. Commun. 2001, 1510.
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21. General procedure for the synthesis of dithiocarbamate
derivatives using mesoporous-Cu catalyst: Representative
experimental procedure for the synthesis of methyl 3-
((phenylcarbamothioyl)thio)propanoate using Cu-MCM-48 as
catalyst (entry 1, Table 4):
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Methyl acrylate (86 mg, 1 mmol) was added in portion to a well
stirred mixture of aniline (93 mg, 1 mmol), carbon disulfide (190
mg, 2. 5 mmol) and Cu-MCM-48 catalyst (20 mg) in ethanol (2
mL) and this mixture was continued to stir at room temperature till
completion of reaction (TLC-monitored). The reaction mixture
was extracted with ethyl acetate (3 × 7 ml) and then the extract
was washed with brine and dried over anhydrous Na2SO4.
Evaporation of the solvent left the crude product which was
purified by column chromatography to provide pure methyl 3-
((phenylcarbamothioyl)thio)propanoate (242.6 mg, 95% yield) as
yellowish solid. A similar protocol was followed for the synthesis
of methyl 3-((phenylcarbamothioyl)thio)propanoate using three
mesoporous Cu materials namely, Cu-MCM-41, Cu-MCM-48 and
Cu-SBA-15. All the products listed in Table 4 were characterized
by their melting point determination and 1H NMR study. These
values are in well accordance with the reported values.11
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