Zirconium tetrakis(dodecyl sulfate) [Zr(DS)4] as an efficient lewis acid-surfactant combined catalyst for the synthesis of quinoxaline derivatives in aqueous media

Article abstract of DOI:10.1080/00397910802406737

Zirconium tetrakis(dodecyl sulfate) [Zr(DS)4] efficiently catalyzes the synthesis of quinoxaline derivatives via the condensation of 1,2-diamines with 1,2-diketones in H2O as a green media at room temperature. Using this method, the title compounds are produced in good to excellent yields and relatively short reaction times. Copyright Taylor & Francis Group, LLC.

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Zirconium Tetrakis(dodecyl
Sulfate) [Zr(DS) ] as an
4
Efficient Lewis Acid–Surfactant
Combined Catalyst for the
Synthesis of Quinoxaline
Derivatives in Aqueous Media
a
b
Alireza Hasaninejad , Abdolkarim Zare
,
c
a
Mohammad Ali Zolfigol & Mohsen Shekouhy
a
Department of Chemistry , Faculty of Sciences,
Persian Gulf University , Bushehr, Iran
b
Department of Chemistry , Payame Noor University
(
PNU) , Bushehr, Iran
c
Faculty of Chemistry , Bu-Ali Sina University ,
Hamedan, Iran
Published online: 27 Jan 2009.
To cite this article: Alireza Hasaninejad , Abdolkarim Zare , Mohammad Ali Zolfigol
&
Mohsen Shekouhy (2009) Zirconium Tetrakis(dodecyl Sulfate) [Zr(DS) ] as an
4
Efficient Lewis Acid–Surfactant Combined Catalyst for the Synthesis of Quinoxaline
Derivatives in Aqueous Media, Synthetic Communications: An International Journal
for Rapid Communication of Synthetic Organic Chemistry, 39:4, 569-579, DOI:
10.1080/00397910802406737
To link to this article: http://dx.doi.org/10.1080/00397910802406737

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1
Synthetic Communications , 39: 569–579, 2009
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910802406737
Zirconium Tetrakis(dodecyl Sulfate) [Zr(DS) ] as
4
an Efficient Lewis Acid–Surfactant Combined
Catalyst for the Synthesis of Quinoxaline
Derivatives in Aqueous Media
1
2
Alireza Hasaninejad, Abdolkarim Zare, Mohammad Ali Zolfigol,
3
1
and Mohsen Shekouhy
1
Department of Chemistry, Faculty of Sciences, Persian Gulf University,
Bushehr, Iran
Department of Chemistry, Payame Noor University (PNU), Bushehr, Iran
2
3
Faculty of Chemistry, Bu-Ali Sina University, Hamedan, Iran
Abstract: Zirconium tetrakis(dodecyl sulfate) [Zr(DS)
synthesis of quinoxaline derivatives via the condensation of 1,2-diamines with
,2-diketones in H O as a green media at room temperature. Using this method,
4
] efficiently catalyzes the
1
2
the title compounds are produced in good to excellent yields and relatively short
reaction times.
2
Keywords: 1,2-Diamine, 1,2-diketone, green chemistry, H O, quinoxaline, zirco-
nium tetrakis(dodecyl sulfate)
The development of simple and efficient chemical processes or methodol-
ogies for the synthesis of biologically active compounds in water is one of
the major challenges for chemists, because water is a safe, very cheap,
[
1]
readily available, and environmentally benign solvent. Although
today’s environmental consciousness imposes the use of water as a
Received August 6, 2008.
Address correspondence to Alireza Hasaninejad, Department of Chemistry,
Faculty of Sciences, Persian Gulf University, Bushehr 75169, Iran. E-mail:
ahassaninejad@yahoo.com or Abdolkarim Zare, Department of Chemistry,
Payame Noor University (PNU), Bushehr 1698, Iran. E-mail: abdolkarimzare@
yahoo.com
5
69

570
A. Hasaninejad et al.
solvent on both industrial and academic chemists, organic solvents are
still used instead of water for mainly two reasons. First, most organic
substances are insoluble in water, and as a result, water does not function
as a reaction medium. Second, many reactive substrates, reagents, and
catalysts are decomposed or deactivated by water. Some of these pro-
blems were solved with the discovery of water-tolerant Lewis acids by
[2]
Kobayashi et al. After that, the successful applications of some Lewis
acid–surfactant combined catalysts (LASC) such as scandium tris(dodecyl
[
3]
[4]
sulfate), aluminum tris(dodecyl sulfate), and the other Metal dodecyl
[
5]
sulfates in organic functional group transformations in aqueous media
have been reported.
Quinoxaline derivatives are an important class of nitrogen-containing
[
6,7]
heterocycles and their importance has been reported in the literature.
For example, they show very interesting pharmacological properties such
[
7a]
[7b]
[7c]
[7d]
as antiprotozoal,
anticancer activities.
antibiotic,
antibacterial,
antifungal,
and
Several synthetic routes have been developed
[
7e,f]
[8]
for the synthesis of quinoxaline derivatives ; however, the most common
method is the condensation of 1,2-diamines with 1,2-dicarbonyl com-
pounds in the presence of catalysts such as ceric(IV) ammonium nitrate,
[9c]
iodine in DMSO,
[
9a]
[9b]
[9d]
[9e]
sulfamic acid,
Yb(OTf) ,
3
oxalic acid,
[
9f]
[9g]
[9h]
o-iodoxybenzoic acid, H P W O ꢀ24H O, KHSO4, and polyani-
6
2
18 62
2
[
9i]
line-sulfate salt. It is worth noting that the methods that have been
established for the preparation of quinoxaline derivatives are associated
with one or more of the following drawbacks: (i) the need for anhydrous
conditions, (ii) the use of expensive catalysts, (iii) unsatisfactory yields, (iv)
long reaction times, (v) harsh reaction conditions, (vi) inefficiency of the
method when aliphatic or aryl 1,2-diamines with electron-withdrawing
substituents are applied in the condensation reaction, and (vii) no agree-
ment with the green chemistry protocols by the use of volatile organic sol-
vents. Furthermore, some methods need cumbersome experimental and
multistep procedures. Therefore, development of an efficient, simple,
cheap, safe, and green method for the preparation of quinoxalines is desir-
able. As part of our program to develop more efficient and environ-
mentally benign methods for organic syntheses using economic and
[
9e,10]
ecofriendly catalysts,
practical method for the preparation of quinoxaline derivatives from
,2-diamines and 1,2-diketones using Zr(DS) in water at extremely mild
in this work, we report a facile, efficient, and
1
4
reaction conditions (Scheme 1). It is important to note that this method
has none of the previously mentioned disadvantages at all.
At first, we studied the reaction of 1,2-benzene diamine (1 mmol)
with benzil (1 mmol) in H O (40 mL) to optimize the reaction conditions
2
with respect to molar ratio of Zr(DS) to the substrate and temperature
4
(Scheme 1, Table 1). We found that 2.5 mol% of Zr(DS) was sufficient to
4

Zirconium Tetrakis(dodecyl Sulfate)
571
Scheme 1. The condensation of 1,2-benzene diamine with benzil.
produce the desired quinoxaline in 94% yield within 30 min at room
temperature (Table 1, entry 4).
Then, the generality and the scope of the procedure was evaluated by
the reaction of a number of aryl and alkyl 1,2-diamines with structurally
and electronically diverse 1,2-diketones. The results are summarized in
Table 2. As it can be seen from Table 2, all reactions proceeded efficiently
and the desired products were produced in good to excellent yields in rela-
tively short reaction times. We investigated the effect of electron-releasing
and electron-withdrawing substituents on the aromatic ring of aryl 1,2-dia-
mines on the reaction. As Table 2 indicates, electron-releasing groups had
no significant effect on the reaction results (Table 2, entries
6
–11); however, electron-withdrawing substituents decreased the yields
and increased the reaction times (Table 2, entries 12 and 13). Moreover,
harsher reaction conditions were needed in these cases. The results also
showed that the structure and the electronic properties of the aromatic ring
of 1,2-diketones had negligible effect on the yields and the reaction times.
Aliphatic 1,2-diamines also afforded the corresponding quinoxalines in
high yields but in harsher reaction conditions (Table 2, entries 15 and 16).
Table 1. Reaction of benzene-1,2-diamine with benzil in the presence of different
molar ratios of Zr(DS) at different temperatures
4
a
Molar ratio of
Zr(DS) (mol%)
Temperature
ꢁ
Time
(min)
Yield
(%)
Entry
4
( C)
1
2
3
4
5
6
7
1
1.5
2
2.5
3
2.5
2.5
rt
rt
rt
rt
rt
90
80
50
30
30
25
15
42
71
91
94
94
95
93
40
60
a
Isolated yield.

572
A. Hasaninejad et al.
Table 2. Synthesis of quinoxalines via the condensation of 1,2-diamines with 1,2-
diketones using Zr(DS) in H O at room temperature
4 2
Mp
ꢁ
a
Time Yield
(min)
( C)
(lit.)
Entry 1,2-Diamine
1
Product
(%)
30
94
129–130
[
130–131)
9e]
(
(
2
3
35
30
93
95
149–151
[
148–150)
9e]
132–134
[
135–137)
9f]
(
4
5
60
35
87
89
55–57
[
9a]
(
56)
127–129
[
9a]
(
131)
6
25
96
116–118
[
117–118)
9f]
(
(
Continued )

Zirconium Tetrakis(dodecyl Sulfate)
573
Table 2. Continued
Mp
ꢁ
a
Time Yield
(min)
( C)
(lit.)
Entry 1,2-Diamine
Product
(%)
7
35
95
139–140
[
9a]
(
137)
8
9
35
25
93
94
128–130
[
125–127)
9f]
(
(
163–165
[
165–167)
9f]
1
1
1
0
1
2
20
15
90
93
94
86
175–177
[
9c]
(
172)
302–304
[
304–306)
9e]
(
b
190–192
[
193–194)
9f]
(
(
Continued )

574
A. Hasaninejad et al.
Table 2. Continued
Mp
ꢁ
a
Time Yield
(min)
( C)
(lit.)
Entry 1,2-Diamine
Product
(%)
b
1
1
1
1
3
4
5
6
110
83
188–190
[
192–194)
9f]
(
30
50
50
93
85
87
184–186
[
187–188)
9a]
(
b
168–170
[
9c]
(
167)
b
155–157
[
9c]
(
158)
a
b
Isolated yield.
This reaction was carried out under reflux conditions.
Ease of recycling of the catalyst is one of the advantages of our
method. For the reaction of benzene-1,2-diamine with benzil, no signifi-
cant loss of the product yield was observed when Zr(DS) was reused
4
after five times (please see Table 3).
In summary, we have introduced a highly efficient catalyst for the
condensation of 1,2-diamines with 1,2-diketones in aqueous media. The
promising points for the presented methodology are efficiency, general-
ity, high yield, short reaction time, ease of handling of the catalyst, clea-
ner reaction profile, ease of product isolation, simplicity, potential for

Zirconium Tetrakis(dodecyl Sulfate)
575
Table 3. Reaction of benzene-1,2-diamine with benzil in
the presence of recycled Zr(DS)
4
a
Yield (%)
Entry
Cycle
Time (min)
1
2
3
4
5
6
—
1
2
3
4
30
30
30
35
45
50
94
95
93
92
94
89
5
a
Isolated yield.
recycling of the catalyst, and finally agreement with the green chemistry
protocols, which all make it a useful and attractive process for the
synthesis of quinoxaline derivatives.
EXPERIMENTAL
All chemicals were purchased from Merck, Fluka, or Aldrich chemical
companies. All known compounds were identified by comparison of their
1
melting points and spectral data with those in the authentic samples. H
1
3
NMR (250 MHz) and C NMR (62.5 MHz) were run on a Bruker
Avance DPX-250, FT-NMR spectrometer (d in ppm). Mass spectra were
recorded on a Shimadzu GC MS-QP 1000 EX apparatus. Microanalyses
were performed on a Perkin-Elmer 240-B microanalyzer. Melting points
were recorded on a B u¨ chi B-545 apparatus in open capillary tubes.
General Procedure for the Synthesis of Quinoxaline Derivatives
A mixture of 1,2-diamine (1 mmol) and 1,2-diketone (1 mmol) was added
to a suspension of Zr(DS) (0.029 g, 0.025 mmol, 2.5 mol%) in water
4
(
40 mL), and the resulting mixture was stirred at room temperature for
the times reported in Table 2. Then, EtOAc (2 ꢂ 10 mL) was added to
the reaction mixture, and the organic phase was separated and dried over
anhydrous Na SO . The solvent was evaporated, and the crude product
2
4
was purified by recrystallization from EtOH. For recovering the catalyst,
aqueous phase and organic phase were centrifuged together which a tri-
phase system (organic, aqueous, and solid phase) was obtained. The solid
phase (catalyst) was separated and dried under reduced pressure and
reused.

576
A. Hasaninejad et al.
Selected Spectral Data of the Products
2
,3-Diphenylquinoxaline (1)
ꢁ
[9e]
ꢁ
1
White solid; mp 129–130 C (lit. mp 130–131 C); H NMR (CDCl ):
3
3
1
d ¼ 7.29–7.33 (m, 6H), 7.51 (m, 4H), 7.77 (m, 2H), 8.21 (m, 2H);
C
NMR (CDCl ): d ¼ 128.1, 128.7, 129.1, 129.9, 131.0, 139.6, 141.7,
3
þ
1
53.2; MS: m=z ¼ 282 (M ); Anal. calcd. for C H N : C, 85.08; H,
2
0
14
2
5
.00; N, 9.92. Found: C, 85.31; H, 4.83; N, 10.11.
9
,10-Dimethylacenaphtho[1,2-b]quinoxaline (11)
ꢁ
[9e]
Yellow solid; mp 302–304 C (lit. mp 304–306 C); H NMR (CDCl ):
ꢁ
1
3
d ¼ 2.51 (s, 6H), 7.78 (m, 2H), 7.89 (s, 2H), 8.03 (m, 2H), 8.34 (m, 2H);
1
3
C NMR (CDCl ): d ¼ 20.3, 121.5, 127.8, 128.0, 128.6, 128.9, 129.1,
3
þ
1
C H N : C, 85.08; H, 5.00; N, 9.92. Found: C, 84.90; H, 5.24; N, 10.13.
39.5, 140.00, 148.5, 153.3; MS: m=z ¼ 282 (M ). Anal. calcd. for
2
0
14
2
2
,3-Diphenylbenzo[g]quinoxaline (14)
ꢁ
[9a]
Yellow solid; mp 184–186 C (lit. mp 187–188 C); H NMR (CDC1 ):
ꢁ
1
3
1
3
d ¼ 7.30–7.34 (m, 6H), 7.48–7.53 (m, 6H), 8.03 (m, 2H), 8.59 (s, 2H);
C
NMR (CDCl ): d ¼ 126.5, 127.4, 128.0, 128.3, 129.0, 129.7, 133.8, 136.9,
3
þ
1
H, 4.85; N, 8.43. Found: C, 86.93; H, 4.70; N, 8.56.
39.4, 153.7; MS: m=z ¼ 332 (M ). Anal. calcd. for C H N : C, 86.72;
2
4
16
2
ACKNOWLEDGMENTS
We appreciate Persian Gulf University and Payame Noor University
Research Councils for the financial support of this work.
REFERENCES
1
. (a) Grieco, P. A. Organic Synthesis in Water; Blackie Academic and Profes-
sional: London, 1998; (b) Anastas, P. T.; Williamson, T. C. (Eds). Green
Chemistry (ACS Symposium Series 626), American Chemical Society:
Washington, DC, 1996; (c) Li, C.-J.; Chan, T.-H. Organic Reactions in Aqu-
eous Media; Wiley: New York, 1997; (d) Anastas, P.; Warner, J. C. Green
Chemistry: Theory and Practice; Oxford University Press, Oxford, 1998; (e)
Li, C.-J. Organic reactions in aqueous media with a focus on carbon–carbon
bond formations: A decade update. Chem. Rev. 2005, 105, 3095–3165.

Zirconium Tetrakis(dodecyl Sulfate)
577
2
. (a) Kobayashi, S.; Manabe, K.; Nagayama, S. Modern Carbonyl Chemistry; J.
Otera (Ed.); Wiley-VCH: Weinheim, 2000; (b) Manabe, K.; Mori, Y.;
Wakabayashi, T.; Nagayama, S.; Kobayashi, S. Organic synthesis inside par-
ticles in water: Lewis acid–surfactant combined catalysts for organic reactions
in water using colloidal dispersions as reaction media. J. Am. Chem. Soc.
2000, 122, 7202–7207; (c) Kobayashi, S.; Nagayama, S.; Busujima, T. Lewis
acid catalysts stable in water: Correlation between catalytic activity in water
and hydrolysis constants and exchange rate constants for substitution of
inner-sphere water ligands. J. Am. Chem. Soc. 1998, 120, 8287–8288.
. (a) Mnabe, K.; Aoyama, N.; Kobayashi, S. Friedel-Crafts-type Conjugate
addition of indoles using a Lewis acid–surfactant combined catalyst in water.
Adv. Synth. Catal. 2001, 343, 174–176; (b) Mori, Y.; Kakumoto, K.; Manabe,
K.; Kobayashi, S. Michael reactions in water using Lewis acid–surfactant
combined catalysts. Tetrahedron Lett. 2000, 41, 3107–3111.
3
4
. (a) Firouzabadi, H.; Iranpoor, N.; Nowrouzi, F. The facile and efficient
Michael addition of indoles and pyrrole to a,ß-unsaturated electron-deficient
compounds catalyzed by aluminium dodecyl sulfate trihydrate
[Al(DS)
H.; Iranpoor, N.; Khoshnood, A. Aluminum tris(dodecyl sulfate) trihydrate
3
2
] ꢀ 3H O in water. Chem.Commun. 2005, 789–791; (b)Firouzabadi,
Al(DS) ꢀ 3H O as an efficient Lewis acid–surfactant combined catalyst for
3
2
organic reactions in water: Efficient conversion of epoxides to thiiranes and
to amino alcohols at room temperature. J.Mol.Cat.A:Chem. 2007, 274,
109–115.
5
. Zolfigol, M. A.; Salehi, P.; Ghaderi, A.; Shiri, M.; Tanbakouchian, Z. An
eco-friendly procedure for the synthesis of polysubstituted quinolines under
aqueous media. J. Mol. Cat. A: Chem. 2006, 259, 253–258.
6
. (a) Brock, E. D.; Lewis, D. M.; Yousaf, T. I.; Harper, H. H. Reactive dyes
and their use. WO 9951688, 1999; (b) Thomas, K. R.; Marappan,V.; Jiann,
T. L.; Chang-Hao, C.; Yu-ai, T. Chromophore-labeled quinoxaline deriva-
tives as efficient electroluminescent materials. Chem. Mater. 2005, 17,
1860–1866; (c) Dailey, S.; Feast, J. W.; Peace, R. J.; Saga, R. C.; Till, S.;
Wood, E. L. Synthesis and device characterisation of side-chain polymer elec-
tron transport materials for organic semiconductor applications. J. Mater.
Chem. 2001, 11, 2238–2243; (d) Jonathan, L. S.; Hiromitsu, M.; Toshisha,
M.; Vincent, M. L.; Hiroyuki, F. Quinoxaline-oligopyrroles: Improved pyr-
role-based anion receptors. Chem. Commun. 2002, 862–863.
7
. Hui, X.; Desrivot, J.; Bories, C.; Loiseau, P. M.; Franck, X.; Hocquemiller,
R.; Figadere, B. Synthesis and antiprotozoal activity of some new synthetic
substituted quinoxalines. Bioorg. Med. Chem. Lett. 2006, 16, 815–820; (b)
Dell, A.; William, D. H.; Morris, H. R.; Smith, G. A.; Feeney, J. Roberts,
G. C. K. Structure revision of the antibiotic echinomycin. J. Am. Chem.
Soc. 1975, 97, 2497–2502; (c) Jaso, A.; Zarranz, B.; Aldana, I.; Monge, A.
Synthesis of new quinoxaline-2-carboxylate1, 4-dioxide derivatives as
anti-Mycobacterium tuberculosis agents. J. Med. Chem. 2005, 48, 2019–
2025; (d) Aguirre, G.; Cerecetto, H.; DiMaio, R.; Gonzales, M.; Alfaro, M.
E. M. A.; Jaso, A.; Zarranz, B.; Ortega, M. A.; Aldana, I.; Monge-Vega,

578
A. Hasaninejad et al.
0
A. Quinoxaline N,N -dioxide derivatives and related compounds as growth in
hibitors of Trypanosoma cruzi: Structure–activity relationships. Bioorg. Med.
Chem. Lett. 2004, 14, 3835–3839; (e) Gali-Muhtasib, H. U.; Diab-Assaf, M.;
Haddadin, M. J. Quinoxaline 1,4-dioxides induce G =M cell cycle arrest and
2
apoptosis in human colon cancer cells. Cancer Chemoth. Pharm. 2005, 55,
369–378; (f) Toshima, K.; Ozawa, T.; Kimura, T.; Matsumara, S. The signif-
icant effect of the carbohydrate structures on the DNA photocleavage of
the quinoxaline-carbohydrate hybrids. Bioorg. Med. Chem. Lett. 2004, 14,
2
777–2779.
. (a) Venkatesh, C.; Singh, B.; Mahata, P. K.; Ila, H.; Junjappa, H. Heteroan-
nulation of nitroketene N,S-arylaminoacetals with POCl : A novel highly
8
3
regioselective synthesis of unsymmetrical 2,3-substituted quinoxalines. Org.
Lett. 2005, 7, 2169–2172; (b) Xekoukoulotakis, N. P.; Hadjiantonious-
Maroulis, C. P.; Maroulis, A. J. Synthesis of quinoxalines by cyclization of
a-arylimino oximes of a-dicarbonyl compounds. Tetrahedron Lett. 2000, 41,
1
0299–10302; (c) Antoniotti, S.; Du n~ ach, E. Direct and catalytic synthesis
of quinoxaline derivatives from epoxides and ene-1,2-diamines. Tetrahedron-
Lett. 2002, 43, 3971–3973; (d) Robinson, R. S.; Taylor, R. J. K. Quinoxaline
synthesis from a-hydroxy ketones via a tandem oxidation process using
catalysed aerobic oxidation. Synlett 2005, 1003–1005; (e) Gopaland, D. V.;
Subrahmanyam, M. Single-stepsynthesis of 2-methylquinoxaline from 1,2-
phenylenediamine and 1,2-propanediol over modified HY zeolites. Catal.
Commun. 2001, 219–223; (f) Staszewska, A.; Stefanowicz, P.; Szewczuk, Z.
Direct solid-phase synthesis of quinoxaline-containing peptides. Tetrahedron
Lett. 2005, 46, 5525–5528; (g) Das, B.; Venkateswarlu, K.; Suneel, K.; Majhi,
A. An efficient and convenient protocol for the synthesis of quinoxalines and
dihydropyrazines via cyclization–oxidation processes using HClO ꢀ SiO as a
4
2
heterogeneous recyclable catalyst. TetrahedronLett. 2007, 48, 5371–5374.
9
. (a) More, S. V.; Sastry, M. N. V.; Yao, C.-F. Cerium (IV) ammonium nitrate
CAN) as a catalyst in tap water: A simple, proficient and green approach for
(
the synthesis of quinoxalines. Green Chem. 2006, 8, 91–95; (b) Bhosale, R. S.;
Sarda, S. R.; Ardhapure, S. S.; Jadhav, W. N.; Bhusare, S. R.; Pawar, R. P.
An efficient protocol for the synthesis of quinoxaline derivatives at room tem-
perature using molecular iodine as the catalyst. Tetra hedron Lett. 2005, 46,
7183–7186; (c) Darabi, H. R.; Mohandessi, S.; Aghapoor, K.;
Mohsenzadeh, F. A recyclable and highly effective sulfamic acid=MeOH
catalytic system for the synthesis of quinoxalines at room temperature.
Catal Commun. 2007, 389–392; (d) Wang, L.; Liu, J.; Tian, H.; Qian, C.
Ytterbium triflate catalyzed heterocyclization of 1,2-phenylenediamines and
alkyl oxalates under solvent-free conditions via Phillips reaction: A facile
synthesis of quinoxaline-2,3-diones derivatives. Synth. Commun. 2004, 34,
1349–1357; (e) Hasaninejad, A.; Zare, A.; Mohammadizadeh, M. R.;
Shekouhy, M. Oxalic acid as an efficient, cheap, and reusable catalyst for
the preparation of quinoxalines via condensation of 1,2-diamines with
a-diketones at room temperature. Arkivoc 2008, 8, 28–35; (f) Heravi, M.
M.; Bakhtiari, K.; Tehrani, M. H.; Javadi, N. M.; Oskooie, H. A. Facile

Zirconium Tetrakis(dodecyl Sulfate)
579
synthesis of quinoxaline derivatives using o-iodoxybenzoic acid (IBX) at
room temperature. Arkivoc 2006, 16, 16–22; (g) Heravi, M. M.; Bakhtiari,
K.; Bamoharram, F. F.; Tehrani, M. H. Wells– Dawson type heteropolyacid
catalyzed synthesis of quinoxaline derivatives at room temperature. Monatsh.
Chem. 2007, 138, 465–467; (h) Oskooie, H. A.; Heravi, M. M.; Bakhtiari, K.;
Taheri, S. An efficient and facile synthesis of quinoxaline derivatives
catalyzed by KHSO4 at room temperature. Monatsh. Chem. 2007, 138,
875–877; (i) Srinivas, C.; Kumar, C. N. S. S. P.; Rao, V. J.; Palaniappan,
S. Efficient, convenient and reusable polyaniline–sulfate salt catalyst for
the synthesis of quinoxaline derivatives. J. Mol. Cat. A: Chem. 2006, 265,
228–231.
1
0. Hasaninejad, A.; Parhami, A.; Zare, A.; Khalafi-Nezhad, A.; Nasrolahi
Shirazi, A.; Moosavi Zare, A. R. Magnesium sulfate as an efficient and very
cheap reagent for the preparation of bis(indolyl)methanes. Polish J. Chem..
2008, 82, 565–569; (b) Zare, A.; Hasaninejad, A.; Khalafi-Nezhad, A.;
Parhami, A.; Moosavi Zare, A. R. A Solvent less protocol for the Michael
addition of aromatic amidest to a,b-unsaturated esters promoted by micro-
wave irradiation. J. Iran. Chem. Soc. 2008, 5, 100–105; (c) Khalafi-Nezhad,
A.; Parhami, A.; Zare, A.; Moosavi Zare, A. R.; Hasaninejad, A.; Panahi,
F. Trityl chloride as a novel and efficient organic catalyst for room tempera-
ture preparation of bis(indolyl)methanes under solvent-free conditions in
neutral Media. Synthesis 2008, 617–621; (d) Hasaninejad, A.; Zare, A.;
Sharghi, H.; Shekouhy, M. P O =SiO : An efficient, green and heterogeneous
2
5
2
catalytic system for the solvent-free synthesis of N-sulfonyl imines. Arkivoc
008, 11, 64–74; (e) Zare, A.; Hasaninejad, A.; Beyzavi, M. H.; Parhami,
2
A.; Moosavi Zare, A. R.; Khalafi-Nezhad, A.; Sharghi, H. Zinc oxide–
tetrabutylammonium bromide tandem as a highly efficient, green, and reusa-
ble catalyst for Michael addition of pyrimidine and purine nucleobases to
a,b-unsaturated esters under solvent-free conditions. Can. J. Chem. 2008,
86, 317–324.