Easy access to quinoxaline derivatives using alumina as an effective and reusable catalyst under solvent-free conditions

Article abstract of DOI:10.1016/j.apcata.2010.12.022

Alumina as a cheap, heterogeneous and reusable catalyst can provide environmentally friendly alternatives for synthesis of quinoxaline derivatives via condensation of 1,2-diamines and 1,2-dicarbonyl compounds under solvent-free conditions. The products could be separated simply from catalyst by filtration and the catalyst could be recycled and reused for several times without noticeably decreasing in catalytic activity.

Full text of DOI:10.1016/j.apcata.2010.12.022

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Applied Catalysis A: General 394 (2011) 48–51
Contents lists available at ScienceDirect
Applied Catalysis A: General
journal homepage: www.elsevier.com/locate/apcata
Easy access to quinoxaline derivatives using alumina as an effective and reusable
catalyst under solvent-free conditions
Maasoumeh Jafarpour∗, Abdolreza Rezaeifard∗, Maryam Danehchin
Catalysis Research Laboratory, Department of Chemistry, Faculty of Science, University of Birjand, Shokatabad, Birjand 97179-414, Iran
a r t i c l e i n f o
a b s t r a c t
Article history:
Alumina as a cheap, heterogeneous and reusable catalyst can provide environmentally friendly alter-
natives for synthesis of quinoxaline derivatives via condensation of 1,2-diamines and 1,2-dicarbonyl
compounds under solvent-free conditions. The products could be separated simply from catalyst by fil-
tration and the catalyst could be recycled and reused for several times without noticeably decreasing in
catalytic activity.
Received 5 September 2010
Received in revised form
11 December 2010
Accepted 16 December 2010
Available online 24 December 2010
© 2010 Elsevier B.V. All rights reserved.
Keywords:
Alumina
Heterogeneous catalyst
Quinoxalines
Solvent-free
Condensation reaction
1. Introduction
catalytic support, precursor to aluminum metal, and as a reagent
in the synthesis of other aluminum-containing compounds such as
Quinoxaline and its derivatives are an important class of benzo-
heterocycles displaying a broad spectrum of biological activities
which have made them privileged structures in pharmacologi-
cally active compounds [1–11], for example several derivatives of
quinoxalines (e.g., HBY-097 and S-2720) display interesting activity
against HIV as non-nucleosidic inhibitors of the reverse transcrip-
tase (RT) [12,13].
aluminum sulfate and fluoride [16].
In continuation of our ongoing program to develop environ-
mentally benign methods [17–20] and using of inorganic solids
[21–24], we would like to report an efficient catalytic method for
the synthesis of quinoxaline derivatives using an inexpensive and
commercially available Al2O3 as a heterogeneous catalyst under
solvent-free conditions (Scheme 1).
In addition to medicinal applications, quinoxaline derivatives
have been found applications as dyes [14], building blocks in the
synthesis of organic semiconductors [15]. Considering the signifi-
cant applications in the fields of medicinal, industrial and synthetic
organic chemistry, there has been tremendous interest in develop-
ing efficient methods for the synthesis of quinoxalines.
Recently, the use of inorganic solids as heterogeneous cata-
lyst have received considerable importance in organic synthesis
because of their ease of handling, enhanced reaction rates, high
selectivity and easy separation of the products that such processes
permitting the recycling and reuse of catalyst with operational and
economical advantages.
2. Experimental
2.1. General remarks
1,2 Diamine, 1,2-dicarbonyl compounds and acidic alumina [90
active acidic (0.063–0.2 mm) for column chromatography] were
purchased from Merck or Fluka Chemical Companies. Progress of
the reactions were monitored by TLC using silica-gel SIL G/UV 254
plates and also by GC on a Shimadzu GC-16A instrument using a
25 m CBP1-S25 (0.32 mm ID, 0.5 ␮m coating) capillary column (see
note for GC analysis). NMR spectra were recorded on a Brucker
Avance DPX 250 MHz and 500 MHz instrument. Mass spectra were
recorded on a Shimadzu GC-MS-QP 5050A.
Of the inorganic solids, alumina is particularly interesting. It has
been used industrially as filler, adsorbent, drying agent, catalyst,
2.2. General procedure for synthesis of quinoxalines in the
presence Al2O3
∗
Corresponding author. Tel.: +98 561 2502516; fax: +98 561 2502515.
E-mail addresses: mjafarpour@birjand.ac.ir (M. Jafarpour),
1,2-Dicarbonyl (1 mmol) and 1,2 diamine (1.5 mmol) were
grinded on 0.2 g of alumina [90 active acidic (0.063–0.2 mm) for
rrezaeifard@gmail.com, rrezaeifard@birjand.ac.ir (A. Rezaeifard).
0926-860X/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2010.12.022

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M. Jafarpour et al. / Applied Catalysis A: General 394 (2011) 48–51
49
R2
R2
R1
N
N
O
O
R1
NH2
NH2
acidic alumina
80°C
+
R2
R2
Scheme 1. Synthesis of quinoxalines in the presence Al2O3 under solvent-free conditions.
Table 1
3. Spectral data
Condensation of o-phenylenediamine and 4,4ꢀ-dimethoxybenzil in the presence and
in the absence of drying agent.a
Table 2, entry 1: M.p. = 123–125 ◦C; 1H NMR (CDCl3, TMS,
500 MHz): ı 7.3 (m, 6H); 7.52 (d, 4H, J = 7.35 Hz); 7.76 (dd, 2H,
J = 3.3 Hz, J = 3.45 Hz) 8.19 (dd, 2H, J = 3.3 Hz, J = 3.45 Hz), ppm; 13C
NMR (CDCl3, TMS, 125 MHz): 128.27, 128.8, 129.26, 129.88, 129.93,
139.18, 141.29, 153.5 ppm; MS (70 eV), m/e: 282 [M+].
Entry
Catalyst
Drying agent
Time (min)
Isolated yield (%)
1
2
3
4
5
6
7
8
Acidic alumina
Acidic alumina
Basic alumina
Basic alumina
Basic alumina
Neutral alumina
Neutral alumina
Neutral alumina
–
25
60
60
60
60
60
60
60
95
65
85
55
45
70
55
45
Na2SO4
–
Na2SO4
Molecular sieve
–
Table 2, entry 2: M.p. = 118–120 ◦C; 1H NMR (CDCl3, TMS,
250 MHz): ı 2.6 (s, 3H); 7.32 (m, 6H); 7.52 (m, 4H); 7.57 (d,
J = 8.75 Hz, 1H); 7.96 (s, 1H); 8.05 (d, J = 8.5 Hz, 1H), ppm; 13C NMR
(CDCl3, TMS, 62.9 MHz): 21.94, 127.06, 128.24, 128.64, 128.71,
129.86, 132.30, 139.24, 139.72, 140.47, 141.30, 152.56, 153.31 ppm;
MS (70 eV), m/e: 296 [M+].
Na2SO4
Molecular sieve
a
The reactions were run at 80 ◦C and the molar ratio of 1,2-dicarbonyl/1,2
diamine/alumina/drying agent was 1:1.5:0.2:0.05 g.
Table 2, entry 3: M.p. = 186–188 ◦C; 1H NMR (CDCl3, TMS,
250 MHz): ı 7.36 (m, 6H); 7.54 (d, J = 6.75 Hz, 4H); 8.26 (d,
J = 9.25 HZ, 1H); 8.49 (d, J = 7 HZ, 1H); 9.05 (s, 1H), ppm; 13C
NMR (CDCl3, TMS, 62.9 MHz): 125.61, 128.46, 129.63, 129.77,
129.82, 129.90, 130.75, 138, 138.07, 139.94, 143.56, 147.84 ppm;
MS (70 eV), m/e: 327 [M+].
column chromatography] for 2 min. By stirring the resulting fine
powder at 80 ◦C the reagents were melted and after appropriate
reaction time (Table 1), the solid product was achieved. After com-
pletion of the reaction monitored by TLC or GC (see note for GC
analysis), the solid product was extracted by adding of ethanol
(3 × 10 ml) followed by filtration. The most of product (>90%) was
precipitated purly by concentrating and cooling of the ethanol.
The remaining product (<10%) was then isolated from excess of
1,2-diamine by plate chromatography eluted with n-hexane/EtOAc
(10/2). Structural assignment of the product was based on its 1H
NMR, 13C NMR and MS spectra (supporting information).
Note: the progress of the reactions for diacetyl derivatives
(entries 7–9 in Table 2) were monitored by GC on a Shimadzu GC-
16A instrument. The GC chromatograms related to entries 7 and 8
are given in supporting information as samples. For example herein
we explain the GC analysis method for entry 7 at 60 min according
to GC chromatogram 1 (supporting information).
Table 2, entry 4: M.p. = 145–147 ◦C; 1H NMR (CDCl3, TMS,
250 MHz): ı 3.83 (s, 6H); 6.86 (d, J = 8.5 Hz, 4H); 7.48 (d, J = 8.5 Hz,
4H); 7.73 (m, 2H); 8.13 (m, 2H), ppm; 13C NMR (CDCl3, TMS,
62.9 MHz): 55.30, 113.77, 128.97, 129.55, 131.25, 131.65, 141.01,
153, 160.16 ppm; MS (70 eV), m/e: 342 [M+].
Table 2, entry 5: M.p. = 125–127 ◦C; 1H NMR (CDCl3, TMS,
250 MHz): ␦ 2.59 (s, 3H); 3.82 (s, 6H); 6.85 (d, J = 8.75 Hz, 4H);
7.46 (d, J = 8.5 Hz, 4H); 7.53 (d, J = 8.5 Hz, 1H); 7.9 (s, 1H), 8.00
(d, J = 8.5 Hz, 1H) ppm; 13C NMR (CDCl3, TMS, 62.9 MHz): 21.87,
55.29, 113.72, 127.8, 128.47, 131.24, 131.78, 131.89, 139.47, 140.04,
141.03, 152.12, 152.82, 160.09 ppm; MS (70 eV), m/e: 356 [M+].
Table 2, entry 6: M.p. = 192–194 ◦C; 1H NMR (CDCl3, TMS,
250 MHz): ı 3.85 (s, 6H); 6.92 (d, J = 8 Hz, 4H); 7.53–7.58 (m, 4H),
8.2 (d, J = 9.25 Hz, 1H), 8.46 (d, J = 9.25 Hz, 1H), 9.01(s, 1H) ppm; 13
C
NMR (CDCl3, TMS, 125 MHz): 55.36, 113.96, 122.87, 125.39, 130.4,
130.62, 131.32, 131.48, 144, 147, 155.18, 155.76, 160.98 ppm; MS
(70 eV), m/e: 387 [M+].
2.2.1. GC conditions
Table 2 entry 7: 1H NMR (CDCl3, TMS, 250 MHz): ı 2.59 (s, 6H);
7.52–7.57 (m, 2H); 7.85–7.89 (m, 2H), ppm; 13C NMR (CDCl3, TMS,
125 MHz): 23.08, 128.21, 128.48, 128.69, 140.95 ppm; MS (70 eV),
m/e: 158 [M+].
- Temperature program: 50 ◦C (3 min). . .. . .30 ◦C/min. . .. . .250 ◦C
(10 min).
- Column: (25 m) CBP1-S25 (0.32 mm ID, 0.5 ␮m coating) capillary
column.
Table 2, entry 8: 1H NMR (CDCl3, TMS, 250 MHz): ı 2.53 (s, 3H);
2.68 (s, 6H); 7.44 (d, J = 8.5, 1H); 7.72 (s, 1H); 7.81 (d, J = 8.25, 1H),
ppm; 13C NMR (CDCl3, TMS, 62.9 MHz): 21.7, 23.12, 127.24, 127.77,
131.00, 139.11, 139.43, 141.06, 152.39 ppm; MS (70 eV), m/e: 172
[M+].
- P: 1 kg/cm2.
We selected the GC chromatogram 1 at 60 min (before the com-
pletion of the reaction) to show clearly the retention times (RT)
of both the reactants and product. GC chromatogram shows three
retention times (RT) at 3.338, 9.718 and 11.337 min for diacetyl,
phenylendiamin and quinoxalin (entry 7) respectively. Conver-
sion and yield determined based on the starting diketone using
“Corrected Area Normalization” method. Accordingly, we used
the peak area of diacetyl (area = 207,496) as limiting reactant and
Quinoxalin (area = 527,840) as sole product. The conversion of the
reaction at 60 min was 71.8%. After 90 min the full conversion was
achieved.
Table 2 entry 9: 1H NMR (CDCl3, TMS, 250 MHz): ı 2.75 (s, 6H);
8.01 (d, J = 9 Hz, 1H); 8.34 (d, J = 9 Hz, 1H); 8.78 (s, 1H), ppm; 13C
NMR (CDCl3, TMS, 62.9 MHz): 23.27, 122.24, 124.79, 129.86, 139.83,
143.63, 147.04, 156.27, 157.21 ppm; MS (70 eV), m/e: 203 [M+].
Table 2, entry 10: 1H NMR (CDCl3, TMS, 250 MHz):
ı
6.71–6.75(m, 4H); 7.88–7.9 (m, 2H); 7.91–7.93 (m, 2H); 8.1–8.13
(m, 2H), ppm; 13C NMR (CDCl3, TMS, 62.9 MHz): 112.02, 113.57,
129.17, 133.64, 142.29, 143.42, 145.19, 150.18 ppm; MS (70 eV),
m/e: 262 [M+].

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50
M. Jafarpour et al. / Applied Catalysis A: General 394 (2011) 48–51
Table 2
Synthesis of quinoxaline derivatives in the presence of alumina under solvent-free conditions.a
R2
R2
R1
acidic alumina
80°C
N
N
O
O
R1
NH2
NH2
+
R2
R2
.
Entry
Diamine R1
1,2-Diketone R2
Product R1, R2
Time (min)
Isolated yield (%)b
Ref.
1
2
3
4
5
6
H
H
H
H
OCH3
OCH3
H, H
CH3, H
NO2, H
H, OCH3
CH3, OCH3
NO2, OCH3
2
4
25
25
75
35
96
95
70c
95
96
45c
[25]
[25]
[25]
[25]
[25]
[25]
CH3
NO2
H
CH3
NO2
OCH3
O
N
d
7
8
9
H
90
45
95
94
96
–
N
O
O
H C
N
d
CH3
NO2
–
N
O
O
O
N
N
d
150
–
N
O
O
N
N
O
O
10
11
H
25
10
25
97
96
83c
[26]
[26]
[27]
O
O
O
O
H
C
N
N
O
O
CH3
O
O
O
O
O
N
N
N
O
O
12
NO2
O
O
O
a
The reactions were run at 80 ◦C and the molar ratio of 1,2-dicarbonyl/1,2 diamine/alumina was 1:1.5:0.2 g.
All products were identified by their spectroscopic data.
Remainder is the starting materials were isolated intact and increase in reaction time did not affect the yield of the products.
Their spectroscopic data have been reported in supporting information.
b
c
d
Table 2, entry 11: 1H NMR (CDCl3, TMS, 250 MHz): ı 2.55 (s, 3H);
under neat conditions which gave 45% yield (NMR) after 7 h .An
increase in the temperature and reaction time did not affect the
yield of the product. Then, similar reaction was studied on differ-
ent supports such as molecular sieves, types of alumina, charcoal,
graphite and silica gel in the absence of solvent. Among these, acid
alumina was found to be highly effective for promoting the con-
densation reaction and 95% of the desired quinoxaline was secured
within 25 min at 80 ◦C under solvent-free conditions using 0.2 g
alumina as an adequate amount of catalyst for 1 mmol of 1,2-
dicarbonyl and 1.5 mmol of 1,2 diamine. It should be mentioned
that the employment of an equimolar ratio of 1,2-dicarbonyl and
1,2 diamine on alumina (0.2 g) in this system, decreased the con-
version of the reaction.
6.52–6.61(m, 4H); 7.52–7.58 (m, 3H); 7.88 (s, 1H); 7.97 (d, J = 8.75,
1H), ppm; 13C NMR (CDCl3, TMS, 62.9 MHz): 21.88, 111.82, 112.55,
127.91, 128.57, 132.74, 139.05, 140.65, 141.79, 142.52, 143.96,
144.09, 150.88 ppm; MS (70 eV), m/e: 276 [M+].
Table 2, entry 12: 1H NMR (CDCl3, TMS, 250 MHz):
ı
6.62–6.66(m, 4H); 7.72–7.78 (m, 2H); 8.6 (d, J = 9.25, 1H); 8.82 (d,
J = 9.25, 1H); 9.03(s, 1H), ppm; 13C NMR (CDCl3, TMS, 62.9 MHz):
112.07, 112.55, 122.8, 125.4, 132, 140.5, 142, 142.9, 144.7, 148, 151,
161 ppm; MS (70 eV), m/e: 307 [M+].
4. Results and discussions
The difference in the catalytic activity of types of alumina in con-
densation of 1,2-diamines and 1,2-dicarbonyl compounds, raises
Preliminary studies were addressed to condensation of o-
phenylenediamine and 4,4ꢀ-dimethoxybenzil as a model reaction

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M. Jafarpour et al. / Applied Catalysis A: General 394 (2011) 48–51
51
Table 3
Acknowledgements
Catalytic activity of alumina in comparison with other catalysts used for condensa-
tion of o-phenylenediamine and benzil.
Support for this work by Research Council of University of Bir-
jand under project 1389/D/206 is highly appreciated.
Entry Catalyst
Catalyst (mol %) Time (min) Yield (%) Ref.
a
1
Al2O3
0.2 g
10
10
10
2 ml
5 wt%
2
15
10
150
20
20
96
96
95
100
96
95
–
CuSO45H2O/H2O
Zn[(l)Proline], HOAc
Mont K-10, H2O
[Hbim]BF4
Polyaniline-sulfate,
CH2Cl2
[25]
[28]
[29]
[30]
[31]
Appendix A. Supplementary data
2
3
4
5
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.apcata.2010.12.022.
6
I2, DMSO
10
35
95
[32]
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In order to show the merit of the present catalytic method
for the synthesis of quinoxalines, we have compared our results
obtained using alumina with some of those reported in the litera-
ture (Table 3).
5. Conclusion
In conclusion, commercially available alumina can provide an
environmentally friendly alternative for easy access to wide variety
of quinoxaline derivatives. The high reusability of alumina which
is easily separated from the reaction media as well as easy and safe
work-up procedure providing ready scalability makes this solvent-
free strategy more attractive for practical goal. Further works in
this area is underway.