Sulfonated porous Carbon (SPC)-catalyzed synthesis of benzothiazole derivatives in water

Article abstract of DOI:10.1080/10426507.2011.631642

A simple and efficient procedure has been developed for the synthesis of benzothiazole derivatives in water by the condensation of 2-aminothiophenol with aldehydes in the presence of Sulfonated porous carbon (SPC). This method provides a simple and effici

Full text of DOI:10.1080/10426507.2011.631642

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Sulfonated Porous Carbon (SPC)-
Catalyzed Synthesis of Benzothiazole
Derivatives in Water
Arash Shokrolahi a , Abbas Zali a & Mohammd Mahdavi a
a Department of Chemistry, Malek-ashtar University of Technology,
Shahin-shahr, I. R. Iran
Version of record first published: 31 Jan 2012
To cite this article: Arash Shokrolahi, Abbas Zali & Mohammd Mahdavi (2012): Sulfonated Porous
Carbon (SPC)-Catalyzed Synthesis of Benzothiazole Derivatives in Water, Phosphorus, Sulfur, and
Silicon and the Related Elements, 187:4, 535-543
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Phosphorus, Sulfur, and Silicon, 187:535–543, 2012
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2011.631642
SULFONATED POROUS CARBON (SPC)-CATALYZED
SYNTHESIS OF BENZOTHIAZOLE DERIVATIVES
IN WATER
Arash Shokrolahi, Abbas Zali, and Mohammd Mahdavi
Department of Chemistry, Malek-ashtar University of Technology,
Shahin-shahr, I. R. Iran
GRAPHICAL ABSTRACT
Abstract A simple and efficient procedure has been developed for the synthesis of benzoth-
iazole derivatives in water by the condensation of 2-aminothiophenol with aldehydes in the
presence of Sulfonated porous carbon (SPC). This method provides a simple and efficient pro-
tocol in terms of mild reaction conditions, clean reaction profiles, small quantity of catalyst,
and simple workup procedure.
Keywords Benzothiazole; sulfonated porous carbon; water; microwaves irradiation
INTRODUCTION
Benzothiazole and its derivatives are found in numerous pharmaceutical agents with
a diverse range of biological properties.1–8 Their significance is also due to their appli-
cations in the treatment of autoimmune, inflammatory, epilepsy, analgesia, viral, cancer,
tuberculosis diseases, and the prevention of organ transplant rejection.1–3
Many methods have been reported in the literature for the synthesis of benzothia-
zoles. Traditional methods include (i) condensation of 2-aminothiophenols with aldehy-
des,4 carboxylic acids,5 acid chlorides,6 esters,7 or nitriles8 and (ii) oxidative cyclization
Received 31 July 2011; accepted 10 October 2011.
Address correspondence to Arash Shokrolahi, Department of Chemistry, Malek-ashtar University of Tech-
nology, Shahin-shahr, P.O. Box 83145-115, I. R. Iran. E-mail: ar shokrolahi@mut-es.ac.ir
535

536
A. SHOKROLAHI ET AL.
of thiobenzanilides using various oxidants.9–14 Recently, a one-step preparation of ben-
zothiazole derivatives by the aqueous reaction of the corresponding thioamidinium salts
and 2-aminothiophenol has been reported.15 However, many of these existing methods are
accompanied by one or more disadvantages such as the use of volatile organic solvents,
costly air sensitive reagents,4a prolonged reaction time,16 multistep reaction sequences,
high reaction temperature, requirement of extreme pH, tedious work-up procedures,4e and
generation of solid wastes.17,18 Therefore, more attention has been directed to overcome
the above limitations by providing an efficient and convenient protocol for the synthesis of
2-substituted benzothiazoles.
Due to environmental and economic considerations in recent years, heterogeneous
catalysts have been gained some advantages with respect to the homogeneous systems,
such as ease of recovery, recycling, and enhanced stability. Porous carbon materials and
products based on them are diffuse in many actual scientific applications. They are used as
supports for different catalytic processes, fuel cells, and capacitors. Porous carbon materials
with high surface areas and well-developed porosities have attracted substantial attention
because they can fulfill most of the desirable properties required for a suitable catalyst
support. The stability in aggressive media at elevated temperature, feasibility of control
parameters of the porous structure surface area in a broad range, and the physicochemical
properties are the major advantages of carbon materials.19–27
The application of microwaves (MW) irradiation as an energy-efficient heat source
for accelerating chemical reactions has been reported in the literatures. Reactions that
previously required hours to run to completion can now be finished within minutes.28,29
Moreover, carrying out organic reactions in water has become highly desirable in
recent years to meet environmental considerations. The use of water as a sole medium of
organic reactions would greatly contribute to the development of environmentally friendly
processes.
Herein, an efficient and convenient procedure for the synthesis of benzothiazole
derivatives in water using Sulfonated Porous Carbon (SPC) as a heterogeneous catalyst
under reflux conditions and microwave irradiation (Scheme 1) is reported.
NH2
SH
SPC/water.
N
S
+
R
RCHO
Reflux or MW
Scheme 1
RESULTS AND DISCUSSION
The reaction of 2-aminothiophenol with benzaldehyde was selected as the model
substrate and studied its synthesis in water using SPC as catalyst, to optimize the reaction
conditions. The results of these optimization experiments are presented in Table 1. The ef-
fect of catalyst loading was studied by carrying out the experiments with different amounts
of SPC, without any catalyst under identical conditions and these results are presented in the
Table 1 (Entries 1–5). In the absence of an acid catalyst, the yield of 2-phenylbenzothiazole
was only 16% in duration 10 h after beginning of reaction at refluxing temperature. In-
creasing the catalyst loading from 0.03 to 0.07 g was found to decrease reaction time

SPC-CATALYZED SYNTHESIS OF BENZOTHIAZOLE DERIVATIVES IN WATER
537
Table 1 The condensation of 2-aminothiophenol with benzaldehyde under different reaction conditions
Refluxa
Yield (%)
Microwaveb
Yieldc (%) c
Entry
Catalyst
Added amount (g)
1
2
3
4
5
—
—
3
61
67
90
92
5
31
46
92
93
SPC
SPC
SPC
SPC
0.03
0.05
0.07
0.1
aAt 90 min, bat 6 min, and cisolated yield.
substantially and further increase of catalyst loading to 0.1 g decreased the reaction time
marginally. When the model reaction was carried out under microwave irradiation, it gave
comparatively higher yields of products in shorter reaction time (Table 1, Entries 1–5).
The protocol developed for the synthesis of 2-arylbenzothiazoles and 2-
arylformylbenzothiazoles consists of the stirred mixture of substrate and catalytic amount
of SPC (0.07 g) in water (3 mL) at refluxing temperature and microwave irradiation.
The catalytic performance of the SPC was investigated for the synthesis of 2-
phenylbenzothiazole in water. The reaction product (2-phenylbenzothiazole) measured as a
function of time at refluxing temperature over the SPC, amorphous sugar catalyst (ASC),30
and protonated Nafion.
The surface areas, acid densities, added amount, and initial rate of 2-
phenylbenzothiazole formation (catalytic activity) for all samples are summarized in
Table 2.
Compared with the heterogeneous catalysts, SPC, ACS, and NR50, the sulfonated
porous carbon with initial rate of 81.6 µmol/min indicate a higher catalytic activity in
2-phenylbenzothiazole formation reaction. The yield of reaction was 90%, 41.7%, and
24.4% for SPC, ACS, and NR50 catalyst, respectively, using the same equivalent H+ at
time 90 min (Table 2). The higher catalytic activity of sulfonated porous carbon is due to
high specific surface area, high acid site density, and high density of mesoporous (which
provide good access to the SO3H groups on the surface of the carbon material).
The generality of this approach has been demonstrated by a facile and effortless
synthesis of a wide variety of 2-substituted benzothiazole as shown in Table 3. All the
substrates studied were smoothly converted to the corresponding benzothiazole without
using additional oxidants.
Table 2 Catalytic activity of the tested catalysts under reflux reaction conditions
Total surface
area (m2/g)
Acid density
(mmol H+/g)a
Added
amount (g)
mmol
H+
Initial formation
Catalyst
rateb (µmol min−1 c
)
Yieldd
SPC
ASC
Nafion
1200
5
<0.1
4.55
3.5
0.9
0.07
0.09
0.35
0.3
0.3
0.3
81.6
46.7
24.0
90
41.7
24.4
aDetermined by titration with NaOH, bunder reflux condition, cthe initial rate of a reaction is the instantaneous
rate at the certain time (30 min) of the reaction, and disolated yield.

538
A. SHOKROLAHI ET AL.
Table 3 The reaction of 2-aminothiophenol with aldehydes in the presence of SPC under reflux conditions
NH2
SH
SPC/water,
N
S
+
R
RCHO
Reflux or MW
_
_
1
2a
o
3a o
Reaction condition
Reflux
Time (min)
Microwave
Entry
1
R
Product
Yielda (%)
90
Time (min)
6
Yielda (%)
92
Ref.
31a
3a
90
2
3
4
5
6
7
8
9
3b
3c
3d
3e
3f
70
86
85
87
87
83
85
90
85
5
14
9
89
85
89
85
85
86
91
85
31b
31a
31c
4b
230
150
70
5
70
5
31d
31a
31e
31a
3g
3h
3i
70
5
100
70
6
5
10
11
3j
70
87
88
5
7
87
90
31a
31b
3k
110
(Continued on next page)

SPC-CATALYZED SYNTHESIS OF BENZOTHIAZOLE DERIVATIVES IN WATER
539
Table 3 The reaction of 2-aminothiophenol with aldehydes in the presence of SPC under reflux conditions
(Continued)
NH2
SH
SPC/water,
N
S
+
R
RCHO
Reflux or MW
_
_
1
2a
o
3a o
Reaction condition
Reflux
Time (min)
Microwave
Entry
12
R
Product
Yielda (%)
79
Time (min)
12
Yielda (%)
81
Ref.
31f
3l
180
180
230
13
14
3m
3n
84
80
11
14
87
83
31f
4f
15
3o
250
77
15
84
4f
aIsolated yield.
As shown in Table 3, a series of 2-substituted benzothiazole was synthesized with the
catalyst SPC at refluxing temperature and microwave irradiation. This procedure is applica-
ble to variety of aromatic and heteroaromatic aldehydes, which produced the corresponding
2-aryl benzothiazoles smoothly and in good yields (Table 3, Entries 1–13).
The substitution groups on the aromatic aldehydes ring (electron-releasing or
electron-withdrawing groups) have no obvious effect on the yields and reaction time under
the above optimal conditions. However, aromatic aldehydes with strongly electron-releasing
groups on aromatic ring such as 4-methoxybenzaldehyde gave the product with good yield
in a longer reaction time (Table 3, Entry 3).
We have also examined the condensation reaction of arylformylaldehyde
with 2-aminothiophenol in the presence of SPC in water for the synthesis of 2-
arylformylbenzothiazoles. The reactions were completed within 230–250 min with good
yields (Table 3, Entries 14, 15). When the same reaction was conducted under microwave
irradiation, it gave good yields of product in a shorter reaction time.
Table 4 compares the efficiency of the SPC with the efficiency of other catalysts
in the synthesis of 2-phenylbenzothiazole obtained by other groups. The data in Table 4
show that some protocols took much longer time (Entries 11, 13, and 15), some used extra
oxidants (Entries 1–4), no recovery catalyst (Entries 5–7,10), or low yields of products
(Entries 11–15).

540
A. SHOKROLAHI ET AL.
Table 4 Comparison of results using SPC catalyst with results obtained with other catalysts in the synthesis of
2-phenylbenzothiazolea
Reaction
Entry
Catalyst
Condition (medium)
Time (min) Yieldb (%)
Ref.
4b
1
2
3
4
CANc (0.1 mmol)/H2O2 (30%, 50 ◦C
4 mmol)
Fe(NO3)3 (0.1 mmol)/H2O2
(30%, 4 mmol)
Co(NO3)2 (0.5 mmol)
6H2O/H2O2 (30%, 1 mmol)
K2S2O8 (1 mmol)-CuSO4
(0.01 mmol)
13
14
15
40
97
97
93
90
50 ◦C
32a
4g
80 ◦C (DMF)
60 ◦C (H2O-SDS)
4h
5
6
7
8
9
CTAB (0.05 mmol)d
β-Cyclodextrin (1 mmol)
NH4Cl (0.7 mmol)
Sulfamic acid (100 mg)
Sulfamic acid (100 mg)
PTSAe (0.1 mmol)
Amberlite-IR 120 (100 mg)
Amberlite-IR 120 (100 mg)
Acidic Al2O3 (100 mg)
Acidic Al2O3 (100 mg)
SSAf (100 mg)
SSA (100 mg)
ASC (30 mg)
ASC (30 mg)
Nafion (116 mg)
Nafion (116 mg)
SPC (23 mg)
SPC (23 mg)
Reflux (H2O)
90
75
30
300
10
90
300
10
300
10
300
10
90
6
98
92
84
58
70
97
51
64
45
57
76
91
41.7
51.5
24.4
31.7
90
4h
32b
32c
32d
32d
32c
32d
32d
32d
50 ◦C (H2O)
Room temperature (CH3OH)
Reflux (H2O)
Under MW (solvent free)
70 ◦C (H2O)
Reflux (H2O)
Under MW (solvent free)
Reflux (H2O)
Under MW (solvent free)
Reflux (H2O)
Under MW (solvent free)
Reflux (H2O)
Under MW (H2O)
Reflux (H2O)
Under MW (H2O)
Reflux (H2O)
10
11
12
13
14
15
16
17
18
19
20
21
22
32d
32d
32d
This Work
This Work
This Work
This Work
This Work
This Work
90
6
90
6
Under MW (H2O)
92
aReaction conditions: the reactions were performed with benzaldehyde (1 mmol) and 2-aminothiophenol,
e
bisolated yield, cceric ammonium nitrate, dcetyltrimethyl ammonium bromide, p-toluenesulfonic acid, and
fsilica sulfuric acid.
To check the reusability and recyclability of the catalyst (SPC), we have carried out
the synthesis of 2-phenylbenzothiazole under similar reaction conditions. The catalyst was
separated by filtration after completion of the reaction. It has also been dried and used
for subsequent experiments after adding fresh substrate and water under similar reaction
conditions. For three catalytic cycles, the yields and reaction times remained the same.
The reaction time was found to increase gradually with the comparable yields of the
2-phenylbenzothiazole in subsequent recycle experiments.
In conclusion, we have developed an aqueous and general efficient method for the
synthesis of 2-substituted benzothiazoles by the condensation of aryl, arylformyl aldehydes
with 2-aminothiophenol in the presence of catalytic amount SPC in water. Compared to
previous reported methods, the present protocol features simple work-up, environmentally
benign, good yields, no requirement of extra oxidants, and use of the cheap catalyst.
EXPERIMENTAL
Chemicals were purchased from Fluka, Merck, and Aldrich chemical compa-
nies. Melting points were measured on an Electrothermal 9100 apparatus. Thin layer

SPC-CATALYZED SYNTHESIS OF BENZOTHIAZOLE DERIVATIVES IN WATER
541
chromatography (TLC) was used to monitor all reactions and all yields refer to isolated
products. 1H NMR spectra were recorded on a Bruker-Avance AQS 300 MHz using tetram-
ethylsilane (TMS) as an internal standard. The specific surface area and mean pore di-
ameter (dp) were calculated from adsorption isotherms of nitrogen at 77 K using the
standard Brunauer–Emmett–Teller (BET) equation and were obtained on a NOVA 2200,
Quantachrome Corporation, Version. Microwave reactions were conducted in a modified
microwave oven fitted with a condenser (Samsung MF 45, Korea).
Preparation of SPC
Pine wood powder was used as starting material in the preparation of porous carbon
material. In a typical procedure, wood powder (10 g) was impregnated with ZnCl2 by
immersion in aqueous solution of HCl (1.0 M, 50 mL) containing ZnCl2 (20 g) under
◦
mechanical agitation at 25 C for 15 h. After that the supernatant liquid was separated
◦
by filtration and the remaining solid was oven dried at 80 C for 24 h. Then, the ZnCl2-
impregnated wood powder was placed in a b◦oat like small size ceramic container and heated
gradually from room temperature to 500 C. The heating gradient was not faster than
◦
◦
10 C min−1. The heating time at maximum heat (500 C) treatment temperature was
1 h. Thereafter, the sample was washed by heating in the aqueous HCl solution (5%,
◦
100 mL) at 100 C for 1 h. Then, the resulting solid was filtered and rinsed with warm
distilled water (50 ◦C) to confirm that the wash solution is free of zinc ions. The resultant
◦
activated porous carbon material was finally dried at 80 C in an oven for approximately
24 h. Then, the activated porous◦carbon material (5 g) was heated for 15 h in oleum (18–
24 wt% SO3, 100 mL) at 150 C under N2 in order to introduce SO3H. After heating
and then cooling to room temperature, distilled water (400 mL) was added to the mixture.
The black precipitate was filtered and repeatedly washed with boiling distilled water until
impurities such as sulfate ions were no longer detected in the wash water. The sample was
finally dried overnight in an oven at 80 ◦C to afford the sulfonated acid catalyst.26,27,32
General Procedure for the Preparation of 2-Substituted Benzothiazoles
A mixture of aldehyde (3 mmol), 2-aminothiophenol (3 mmol), SPC (0.07g), and
water (3 mL) was stirred at specified times under reflux condition or microwave irradiation
(at 180 W) (Table 3). The reaction was monitored by TLC. After completion of the reaction,
the product was extracted with ethyl acetate (3 × 10 mL). The organic layer dried over
Na2SO4 and the solvent was removed under reduced pressure. The residue was subjected
to column chromatography on silica gel (300–400 mesh) using an ethyl acetate/petroleum
ether mixture as the eluent to afford a pure product. When necessary, the crude products
were purified through recrystallization from 95% ethanol.
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