ZnO-beta zeolite mediated simple and efficient method for the one-pot synthesis of quinoxaline derivatives at room temperature

Article abstract of DOI:10.2478/s11532-009-0151-7

A rapid and an efficient one-pot method for the synthesis of quinoxalines catalysed by ZnO-beta zeolite at room temperature is described. This environmentally benign method provides several advantages over methods that are currently employed such as a simple work-up, mild reaction conditions, good to excellent yields, and a process to recover and reuse the catalyst for several cycles with consistent activity. Versita Warsaw and Springer-Verlag Wien 2010.

Full text of DOI:10.2478/s11532-009-0151-7

Cent. Eur. J. Chem. • 8(2) • 2010 • 320–325
DOI: 10.2478/s11532-009-0151-7
Central European Journal of Chemistry
ZnO-beta zeolite mediated simple and efficient
method for the one-pot synthesis of quinoxaline
derivatives at room temperature
Research Article
1
2
1
Santosh S. Katkar , Pravinkumar H. Mohite , Lakshman S. Gadekar ,
1
1*
Balasaheb R. Arbad , Machhindra K. Lande
1
Department of Chemistry, Dr. Babasaheb Ambedkar Marathwada University,
Aurangabad-431 004, (MS), India
2
Chemical Engineering and Process Development Division,
National Chemical Laboratory, Pune-411 008, (MS), India
Received 25 July 2009; Accepted 20 October 2009
Abstract: ꢀA ꢀrapidꢀandꢀanꢀefficientꢀone-potꢀmethodꢀforꢀtheꢀsynthesisꢀofꢀquinoxalinesꢀcatalysedꢀbyꢀZnO-betaꢀzeoliteꢀatꢀroomꢀtemperatureꢀisꢀ
described.ꢀThisꢀenvironmentallyꢀbenignꢀmethodꢀprovidesꢀseveralꢀadvantagesꢀoverꢀmethodsꢀthatꢀareꢀcurrentlyꢀemployedꢀsuchꢀasꢀ
aꢀsimpleꢀwork-up,ꢀmildꢀreactionꢀconditions,ꢀgoodꢀtoꢀexcellentꢀyields,ꢀꢀandꢀaꢀprocessꢀtoꢀrecoverꢀandꢀreuseꢀtheꢀcatalystꢀforꢀseveralꢀcyclesꢀ
withꢀconsistentꢀactivity.
Keywords: ZnO-beta zeolite • Quinoxaline • Room temperature • Cyclocondensation
©
Versita Sp. z o.o.
In addition, they are used in the agricultural field as
fungicides, herbicides, and insecticides [22].
1
.Introduction
The importance and utility of quinoxaline derivatives
have led to the development of numerous synthetic
routes. The most common method is the condensation
of aromatic 1,2-diamines with 1,2-dicarbonyl compounds
refluxing in ethanol or acetic acid [23]. Improved methods
have been reported for the synthesis of quinoxaline
derivatives including a bi-catalyzed oxidative coupling
method [24], a microwave procedure [25] and the use
of RuCl -(PPh ) - TEMPO [26], MnO [27], POCl [28],
Zeolites have been used as catalysts in the petroleum
refining, chemical [1], and fine chemical industries [2].
The catalytic activity of H-beta zeolite can be adjusted
by ion exchange with metal ions, acid treatment
and hydrothermal treatment [3,4]. In particular, Zinc
loaded zeolites are suitable catalysts for the organic
transformations, such as Heck reaction [5], propane
aromatization [6], dehydrogenation of small paraffins
2
3
3
2
3
[
7], hydroamination [8-10], aromatization of in situ
generated ethylene [11] and hydration of acetylene
12,13].
Quinoxaline derivatives have attracted the attention
iodine [29], cerium ammonium nitrate [30], CuSO •5H O
4
2
[
31], montmorillonite K-10 [32], H P W O •24H O [33],
6 2 18 62 2
[
SA/MeOH [34], polyaniline sulphate salt [35], Zn [L]
Proline [36]. Some of these methods suffer from one
or more drawbacks, such as long reaction times, low
yields, harsh reaction conditions and tedious workup
procedure. Therefore, development of an efficient and
versatile method is still required.
of organic chemists due to their wide ranging biological
activities including anticancer [14], antiviral [15]
and antibacterial [16]. Also, quinoxaline moieties have
found applications in dyes [17], building blocks in the
synthesis of organic semiconductors [18], chemically
controllable switches [19], dehydroannulenes [20],
anti-inflammatory, anti-protozoal and anti-HIV [21].
As a part of our continued interest [37] in the
development of highly expedient methods for the
*
E-mail: mkl_chem@yahoo.com
320

S. S. Katkar et al.
R1
R1
2.2. Catalyst characterization
The X-ray diffraction (XRD) patterns were recorded
on Bruker 8D advance X-ray diffractometer using
O
N
N
R2
H N
R2 ZnO-beta zeolite
2
O
EtOH, rt
H N
2
R1
R1
monochromator Cu-Kα radiation (40 Kv and 30 mv) of
1
1
2
3
wavelength=1.5405 A°. Conventional scanning electron
microscopy (SEM) images were obtained on JEOL;
JSM-6330 LA operated at 20.0 kV and 1.0000 nA. The
chemical composition of the sample was determined
by energy-dispersive X-ray spectroscopy (EDS) on
a JEOL, JSM-6330. BET surface area has been
Scheme 1. Synthesis of quinoxaline derivatives catalyzed by
ZnO-beta zeolite at room temperature.
synthesis of heterocyclic and biological important
compounds. Herein, we report the first use of zinc
modified beta zeolite as a solid acid catalyst for the
synthesis of quinoxalines under benign reaction
conditions. Our results demonstrate that ZnO-beta
zeoliteisaveryeffective,environmentallyfriendlycatalyst
for the one-pot condensations of o-phenylenediamine
and benzil to form quinoxaline derivatives in excellent
yields (Scheme 1).
measured by means of N adsorption at 77 K preformed
2
on
a
Quantachrome CHEMBET 3000 instrument.
Desorption (TPD)
Temperature-Programmed
measurements were carried out on a Quantachrome
CHEMBET 3000 TPR/TPD instrument.
2
.3. General procedure for the synthesis of
quinoxaline derivatives catalyzed by ZnO-
beta zeolite
2
. Experimental Procedure
A mixture of 1,2-diamine (10 mmol), benzil (10 mmol),
and catalytic amount of ZnO-beta zeolite (0.1 g)
was taken in ethanol (10 mL) and stirred at room
temperature for the appropriate reaction time (Table 2).
The progress of the reaction was monitored by thin layer
chromatography using pet ether, ethyl acetate as solvent
system. After completion of the reaction, the reaction
mass was filtered, the filtrate was concentrated under
reduced pressure, and the crude product obtained was
crystallized from ethanol to afford pure products.
Melting points were taken in an open capillary and
are uncorrected. IR spectra were recorded on Jasco
FT-IR-4100, Japan, in KBr disc. All Chemicals were
purchased either from Merck or Fluka and used without
1
further purification. H NMR spectra were recorded on an
80 MHz and 400 MHz FT-NMR spectrometer in CDCl3
as a solvent and chemical shifts values are recorded
in δ (ppm) relative to tetramethylsilane (Me Si) as an
4
internal standard.
2
.1. Preparation of catalyst
2
.4. Spectroscopic data
In a typical synthesis, tetraethyl orthosilicate (TEOS),
was added to a mixture of tetraethyl ammonium
hydroxide (TEAOH), sodium hydroxide (NaOH) and
an aqueous solution of aluminium sulphate (Al (SO ) )
2
,3-diphenylquinoxaline (3a)
-1
1
IR (cm ) 1596, 1514, 1448, 1346. H NMR (CDCl , 80
MHz) δ 8.20 (m, 2H), 7.76 (m, 2H), 7.56 (m, 4H), 7.35
3
2
4 3
+
(m, 6H); m/z (EI) 282 (M )
and stirred at room temperature for 24 h. Then this
mixture hydrothermally treated at 120°C for 96 h in
autoclavable bottle. After this mixture was cooled at
room temperature solid material obtained was filtered
and washed with deionised water, dried at 80°C for 6 h
and calcined at 550°C for 12 h. H-form of beta zeolite
was prepared through ion exchange of the above
sample with 1M ammonium acetate solution at 80°C
for 10 h. The ion exchange procedure was repeated
twice and the resulting product was calcined at 550°C
for 8 h. Beta zeolite was modified by mixing H-form of
respective zeolite with aqueous solution of zinc acetate.
The mixture was digested at 80°C for 8 h, dried and
calcined at 550°C for 8 h.
6
-Methyl-2,3-diphenylquinoxaline (3b)
1
H NMR (CDCl , 400 MHz) δ 8.14 (d, 1H), 8.03 (s, 1H),
3
7.63 (d, 1H), 7.54 (m, 4H), 7.35 (m, 6H), 2.64 (s, 3H)
6
-Nitro-2,3-diphenylquinoxaline (3c)
1
H NMR (CDCl , 400 MHz) δ 9.10 (d, 1H), 8.57 (m, 1H),
3
8.32 (d, 1H), 7.58 (m, 4H), 7.42 (m, 6H)
2
, 3 Bis (4-methoxy-phenyl) quinoxaline (3d)
1
H NMR (CDCl , 400 MHz) δ 8.15 (m, 2H), 7.68 (m, 2H),
3
7.55 (d, 4H). 6.89 (d, 4H). 3.81 (s, 6H).\
2
, 3 Bis (4-methoxy-phenyl)-6-nitroquinoxaline (3e)
1
H NMR (CDCl , 400 MHz) 9.1 (d, 1H), 8.49 (dd, 1H).
3
8.24 (d, 1H), 7.56 (m, 4H), 6.98 (d, 4H), 3.9 (s, 6H).
3
21

ZnO-beta zeolite mediated simple and efficient
method for the one-pot synthesis of quinoxaline
derivatives at room temperature
2
,3-Bis(4-methoxy-phenyl)-6-methylquinoxaline (3f)
1
H NMR (CDCl , 400 MHz) δ 8.05 (d, 1H), 7.92 (s, 1H),
3
7.58 (d, 1H), 7.48 (d, 4H), 6.9 (d, 4H) 3.9 (s, 6H), 1.58
(s, 3H)
2
,3-Bis(4-chlorophenyl) quinoxaline (3g)
1
H NMR (CDCl , 400 MHz) δ 7.39 (d, 4H), 7.51 (d, 4H),
3
7.83 (dd, 2H), 8.20 (dd, 2H)
2
,3-Bis(4- chlorophenyl)-6-methylquinoxaline (3h)
1
H NMR (CDCl , 400 MHz) δ 7.95 (d, 1H), 7.85 (s,1H),
3
7.65 (d, 1H), 7.51 (d, 4H), 7.05 (d, 4H), 1.50 (s, 3H).
2
.5. XRD analysis
Figure 1. XRD patterns of H-beta zeolite and ZnO-beta zeolite.
Fig. 1 shows the XRD pattern of H-beta and ZnO-beta
zeolite. The powder XRD pattern is the typical type
for H-beta zeolite by comparing it with the reference
beta zeolite [38]. There is no visible difference
observed between synthetic H-beta zeolite and zinc
modified beta zeolite, only the intensity of the peaks
decreases than the parent zeolite. It is clear that samples
contain typical diffraction peaks of H-beta zeolite
(2θ =7.8° and 22.3°).
2
.6. FT-IR analysis
The FT-IR spectra of H-beta zeolite and ZnO-beta
zeolite are shown in Fig. 2. Synthesized material shows
IR bands in the range 550-650 cm usually indicating
the presence of zeolite like material. Peaks around
Figure 2. FT-IR spectra of H-beta zeolite (a) and ZnO-beta
-1
zeolite (b).
-
1
-1
5
75, 525 cm (567 and 517 cm in present work)
-1
correspond to H-beta zeolite [39] and peak at 619 cm
for the structure-sensitive double five-ring vibration. The
characteristic vibrations of H-beta zeolite around 465,
1
4
27 cm also observed. In zinc modified beta zeolite,
-1
the disappearance of the peak at 619 cm is the only
change observed.
2
.7. SEM-EDS analysis
Figure 3. SEM micrograph of (A) H-beta zeolite, (B) ZnO-beta
zeolite.
SEM images of H-beta zeolite and ZnO-beta zeolite are
shown in Fig. 3. It shows that interconnected porous
structures by agglomerating of tiny particles of ZnO on
H-beta zeolite with an average particle size less than
10 μm (Fig. 3b). From EDS analysis zinc content in
modified beta zeolite is 2.75 mass % (Fig. 4).
2
.8. NH -TPD and BET analysis
3
TPD measurements were carried out by (i) pre-treating
of samples from room temperature to 200°C and gas
flow of nitrogen; (ii) adsorption of ammonia at room
temperature; (iii) Desorption of adsorbed ammonia
-1
with an heating rate 10°C min starting from the
adsorption temperature to 700°C.
Figure 4. EDS spectrum of ZnO-beta zeolite.
322

S. S. Katkar et al.
Table 1. The acid strength and surface area of catalyst.
-1
a
Acidity (mmol g )
Total acidity
Catalyst
Surface area
2 -1 b
-1
(
mmol g )
(m g )
Weak (T1)
Strong (T2)
ZnO-beta zeolite
0.703
0.549
0.154
137.13
a
Desorption temperature: T = 100-300°C, T = 300-700°C.
Calculated from BET.
1
2
b
Table 2. Optimization of reaction conditions in the synthesis of C H CH Cl gave low yield of products in 90 min and
6
6,
2
2
a
2, 3-diphenylquinoxaline.
1
20 min respectively (Table 2 entries 3 and 4) while
b
MeOH and MeCN gave moderate yield of products
within 50 min and 20 min respectively (Table 2,
entries 1 and 2). Reactions in EtOH with 0.1 g of
ZnO-beta zeolite proved to be the optimized reaction
condition, affording 98% yield of product (Table 2,
entry 5). To investigate the role of catalyst, the same
reaction was carried out in the absence of catalyst but
the reaction did not yield of product even after 8 h, which
indicates that catalyst is obviously necessary for the
reaction. Same model reaction is carried out by using
of 0.1 g of H-beta zeolite in EtOH gave 73% yield of
product within 25 min.
Entry
Solvent Catalyst
Time (min)
Yield (%)
amount (g)
1
MeOH
MeCN
C H
0.05
75
50
50
48
56
56
0
0
.1
.2
2
3
4
5
a
0.05
40
20
20
69
76
76
0
0
.1
.2
0.05
120
90
90
29
35
35
6
6
0
0
.1
.2
CH Cl
0.05
155
120
120
29
40
40
2
2
0
0
.1
.2
EtOH
0.05
60
8
8
40
98
95
Using the optimized reaction conditions, a range
of substituted quinoxalines were synthesized 3a-h
0
0
.1
.2
(Table 3). It can be seen that in all cases the difference
Reaction was carried out in presence of ZnO-beta zeolite at RT
Isolated yields.
b
in yield of products were very little and both substituted
aromatic diamines such as 4-nitro and 4-methyl gave
The acidity of ZnO-beta zeolite detected by the excellent yields of products with different substituted
temperature programmed desorption of ammonia (NH3- diketones in short reaction times.
TPD). Total acidity and calculated BET surface area of
ZnO-beta zeolite is summarized in Table 1.
Based upon these experiments, we examined the
recycling performance of ZnO-beta zeolite using the
same model reaction. After the separation of products,
the catalyst was washed with n-hexane, dried at 80°C
and reused for next run. The data listed in Table 4 shows
3
. Results and Discussion
In order to get best experimental results, we have that the ZnO-beta zeolite could be reused at least four
considered the model reaction of o-phenylenediamine times without significant loss in catalytic activity. The
(
10 mmol) and benzil (10 mmol) in different solvents ability to easily recycle the catalyst without loss of activity
as well as different catalyst amount (Table 2). is also an attractive property for the environmental and
The choice of solvent proved critical.
Reactions in economic reasons.
a
Table 3. Synthesis of quinoxaline derivatives in presence of ZnO-beta zeolite .
M. P. (°C)
Entry
R1
R2
Time(min)
Yield (%)
Found
127-128
118-119
192-193
151-152
194-195
126-127
194-195
180-181
Reported
3
a
b
H
H
H
Me
NO2
H
08
09
18
09
20
12
08
11
98
96
92
98
90
95
98
92
126-127 [31]
116-117 [31]
193-194 [31]
151-152 [31]
192-194 [31]
125-127 [31]
195-196 [32]
3
3
c
H
3
d
e
OMe
OMe
OMe
Cl
3
NO2
Me
H
3
f
3
g
h
3
Cl
Me
180
[32]
a
1
Yield refer to isolated products, which were characterized by comparing IR , H-NMR , mass spectral data and melting points with those reported
in literature.
3
23

ZnO-beta zeolite mediated simple and efficient
method for the one-pot synthesis of quinoxaline
derivatives at room temperature
Table 4. Reusability of ZnO-beta zeolite catalyst for the synthesis of
Table 5. Comparison of ZnO-beta zeolite with other catalyst for the
a
a
2
, 3-diphenylquinoxaline (Table 3, Entry 1).
synthesis of 2,3 diphenylquinoxaline (Table 3, Entry 3a) .
Entry
Cycle
1
2
3
Second
97
4
Entry Catalyst/Solvent
Time Yield
Refer-
ence
(min)
(%)
Fresh
98
First
98
Third
96
1
2
3
4
5
ZnO-beta/EtOH
8
98
Present
[35]
Yield (%)
Polyaniline sulphate salt/CH Cl2
20
95
2
a
All reactions carried out at RT in EtOH
Isolated yields.
CuSO .5H O/CH COOH
10
95
[31]
b
4
2
3
I2/DMSO
35
95
[29]
A comparison of the catalytic efficiency of ZnO-
beta zeolite with selected previously known catalysts
is collected in Table 5 to demonstrate that the present
protocol is indeed superior to several of the other
protocols. Most of the protocols listed take either longer
reaction times or use high temperatures.
Mont. K-10/water
150
100
[32]
a
All reaction was carried out at RT
Isolated yields.
b
Acknowledgements
The authors are thankful to the Head, Department of
Chemistry, Dr. Babasaheb Ambedkar Marathwada
University,Aurangabad-431004(MS), Indiaforproviding
4
. Conclusion
In summary, the present study confirms the applicability the laboratory facility.
of modified beta zeolite as an effective and reusable
catalyst for one-pot synthesis of quinoxalines. The
proposed method has several benefits, such as short
reaction time, mild reaction condition, easy work-up
procedure and minimum amount of catalyst loading.
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