Zr(HSO4)4 as an efficient catalyst for the preparation of 10-aryl-6,8-dimethyl-6,10-dihydro-5-oxa-6,8-diazaanthra[2,3-d][1, 3]dioxole-7,9-diones under solvent-free conditions

Article abstract of DOI:10.1590/s0103-50532011000700006

A one-pot three-component condensation of 3,4-methylenedioxyphenol, aromatic aldehydes, and 1,3-dimethylbarbituric acid, efficiently promoted in the presence of Zr(HSO₄)₄ under solvent-free conditions, produced 10-aryl-6,8-dimethyl-6

Full text of DOI:10.1590/s0103-50532011000700006

J. Braz. Chem. Soc., Vol. 22, No. 7, 1236-1240, 2011.
Printed in Brazil - ©2011 Sociedade Brasileira de Química
0103 - 5053 $6.00+0.00
Article
A
Zr(HSO4)4 as an Efficient Catalyst for the Preparation of 10-Aryl-6,8-dimethyl-6,10-
dihydro-5-oxa-6,8-diazaanthra[2,3-d][1,3]dioxole-7,9-diones under
Solvent-Free Conditions
Jiangli Zhang,a Wei Lin Lib and Li Qiang Wu*,b
aThe Department Psychology of the Second Affiliated, Xinxiang Medical University,
453000 Xinxiang, Henan, P. R. China
bSchool of Pharmacy, Xinxiang Medical University, 453000 Xinxiang, Henan, P. R. China
A condensação de três componentes “one pot” de 3,4-metilenodioxifenol, aldeídos aromáticos, e
ácido 1,3-dimetilbarbitúrico, eficientemente promovida na presença de Zr(HSO4)4, livre de solvente,
produziu 10-aril-6,8-dimetil-6,10-diidro-5-oxa-6,8-diazaantra[2,3-d][1,3]dioxol-7,9-dionas. O
método oferece diversas vantagens incluindo a simplicidade, facilidade e limpeza do procedimento
extrativo, tempos de reação relativamente curtos e bons a altos rendimentos dos produtos.
A one-pot three-component condensation of 3,4-methylenedioxyphenol, aromatic aldehydes,
and 1,3-dimethylbarbituric acid, efficiently promoted in the presence of Zr(HSO4)4 under solvent-
free conditions, produced 10-aryl-6,8-dimethyl-6,10-dihydro-5-oxa-6,8-diazaanthra[2,3-d][1,3]
dioxole-7,9-diones. The method offers several advantages including simple, easy and clean work-up
procedure, relatively short reaction times and good to high yields of the products.
Keywords: benzo[1,3]dioxoles, 3,4-methylenedioxyphenol, Zr(HSO4)4, solvent-free
Introduction
the ability to oxidize alcohols to the corresponding carbonyl
compounds.13
Benzo[1,3]dioxoles constitute a major class of
naturally occurring compounds,1 and interest in their
chemistry continues unabated because of their wide range
of biological and therapeutic properties such as spasm,2
synergistic,3 antitumour,4 antimicrobial,4 anti-proliferative,5
antioxidant,1,6 anti-inflammatory,6 anti-HIV,7 antineoplastic
and antiviral activities.8 Considering the above reports, the
development of new and simple synthetic methods for the
efficient preparation of new benzo[1,3]dioxoles is therefore
an interesting challenge.
Pyrano[2,3-d]pyrimidines and chromeno[2,3-d]
pyrimidines are two ‘privileged medicinal scaffolds’which
are used for the development of pharmaceutical agents of
various applications. Compounds with these motifs show a
wide range of pharmacological activities such as antiviral,9
antimicrobial,10 antifungal,11 anticonvulsant and analgesic
activities.12 Moreover, they are also useful reagents in
organic synthesis, for example, 5-deaza-10-oxaflavin has
In recent years, metal hydrogen sulfates have been
used as efficient reagents in organic chemistry.14 A broad
range of reactions including deprotection, oxidation,
C–C, C–N and C–O bond formation and cleavage took
place in the presence of these reagents under mild and
heterogeneous conditions. In addition, stability, cheapness,
ability to produce highly efficient products in a short time
and in many cases reusability are among other important
advantages of these reagents.
We herein report that Zr(HSO4)4 efficiently catalyzes the
one-pot syntheses of 10-aryl-6,8-dimethyl-6,10-dihydro-
5-oxa-6,8-diazaanthra[2,3-d][1,3]dioxole-7,9-diones by
condensation of 3,4-methylenedioxyphenol, aromatic
aldehydes, and 1,3-dimethylbarbituric acid under solvent-
free conditions (Scheme 1).
Results and Discussion
Initially, we conducted the reaction of 3,4-methylene-
dioxyphenol, benzaldehyde, and 1,3-dimethylbarbituric
acid in the presence of various metal hydrogen sulfates such
*e-mail: wliq870@163.com

Vol. 22, No. 7, 2011
Zhang et al.
1237
R
10
O
9
O
1
O
11
4
8
N
O
O
Zr(HSO4)4 (10 mol%)
neat, 100 οC
N
+
+ RCHO
OH
2
7
O
O
N
O
O
N
O
3
6
5
1
2
3
4
Scheme 1.
Table 2. Synthesis of 10-phenyl-6,8-dimethyl-6,10- dihydro-5-oxa-6,8-
diazaanthra[2,3-d][1,3]dioxole-7,9-dione under various conditionsa
as NaHSO4, Mg(HSO4)2, Fe(HSO4)3, Zr(HSO4)4,Al(HSO4)3
separately at 100 °C under solvent-free conditions. The
corresponding 10-phenyl-6,8-dimethyl-6,10-dihydro-5-
oxa-6,8-diazaanthra[2,3-d][1,3]dioxole-7,9-dione was
formed in 49, 65, 58, 89 and 79% yield (Table 1). Zr(HSO4)4
was thus selected as the most effective catalyst to carry out
this reaction.
Entry
1
Zr(HSO4)4 Temperature / oC time / min Yield / (%)b
0
100
100
100
25
120
90
0
2
1
34
66
0
3
5
60
4
10
10
10
10
10
10
15
15
20
120
120
60
Table 1. Synthesis of 10-phenyl-6,8-dimethyl-6,10- dihydro-5-oxa-6,8-
diazaanthra[2,3-d] [1,3]dioxole-7,9-dione using metal hydrogen sulfatesa
5
50
30
73
89
88
88
72
86
86
6
90
7
100
110
120
90
45
Entry
Metal hydrogen
sulfates
time / min
Yield / (%)b
8
45
9
45
1
2
3
4
5
6
-
120
90
60
90
45
45
0
10
11
12
60
NaHSO4
49
65
58
89
79
100
45
Mg(HSO4)2
Fe(HSO4)3
Zr(HSO4)4
Al(HSO4)3
100
45
aReaction conditions: 3,4-methylenedioxyphenol (1 mmol); benzaldehyde
(1 mmol); 1,3-dimethylbarbituric acid (1 mmol); neat. bIsolated yield.
aReaction conditions: 3,4-methylenedioxyphenol (1 mmol); benzaldehyde
(1 mmol); 1,3-dimethylbarbituric acid (1 mmol); metal hydrogen sulfates
(0.1 mmol); neat; 100 °C. bIsolated yield.
in their 13C nuclear magnetic resonance (NMR) spectra, and
two distinguishing peak at d 97.9-98.4 ppm for C-4, 11.
Table 3. Preparation of 10-aryl-6,8-dimethyl-6,10- dihydro-5-oxa-6,8-
diazaanthra[2,3-d][1,3]dioxole-7,9-dionesa
Next, to optimize the amount of catalyst and the reaction
temperature, the reaction of 3,4-methylenedioxyphenol,
benzaldehyde and 1,3-dimethylbarbituric acid was studied
under solvent-free conditions in the presence of Zr(HSO4)4
at different temperatures. The results are summarized
in Table 2, and showed that the reaction using 10 mol%
Zr(HSO4)4 at 100 °C proceeded in highest yield.
With this optimized procedure in hand, the scope of
application of this three-component reaction was examined
using different aldehydes as staring materials. As seen from
Table 3, aromatic aldehydes having electron-donating as well
as electron-withdrawing groups were uniformly transformed
into the corresponding 10-aryl-6,8-dimethyl-6,10-dihydro-
5-oxa-6,8-diazaanthra [2,3-d][1,3]dioxole-7,9-diones in
high to excellent yields within 60 min. Substituents on the
aromatic ring had no obvious effect on yield or reaction
time under the above optimal conditions (Table 3). All of
the products 4a-4i exhibited a singlet in their 1H spectra at
d 4.98-5.58 ppm for H-10, two doublets at d 5.90-5.98 ppm
for –OCH2O– and two singlets at d 6.44-6.71 ppm for H-4
and H-11.A distinguishing peak at d 38.2-39.2 ppm for C-10
Entry
R
time / min
Product
4a
Yield / (%)b
1
2
3
4
5
6
7
8
9
C6H5
45
40
35
60
35
40
50
50
40
89
91
87
82
93
89
87
88
90
4-Cl-C6H4
4-F-C6H4
4b
4c
4-Me-C6H4
4-NO2-C6H4
3-NO2-C6H4
2,4-Cl2-C6H3
3,4-Cl2-C6H3
2-Cl-C6H4
4d
4e
4f
4g
4h
4i
aReaction conditions: 3,4-methylenedioxyphenol (1 mmol); aldehyde
(1 mmol); 1,3-dimethylbarbituric acid (1 mmol); Zr(HSO4)4 (0.1 mmol);
100 °C; neat. bIsolated yield.
The plausible mechanism of the reaction is shown in
Scheme 2. It is conceivable that Zr(HSO4)4 catalyzes the
formation of a carbocation in a reversible reaction with the
aromatic aldehyde. The higher reactivity of the carbocation

1238
Zr(HSO4)4 as an Efficient Catalyst for a solvent free one-pot three-component condensation
J. Braz. Chem. Soc.
O
N
O
Ar
O
N
HO
N
O
3
H+
–H2O, +H+
O
O
N
Ar
Ar
HO
HO
N
–H+
H
O
N
OH
HO
O
O
OH
6
2
5
1
Ar
O
Ar
O
N
H
–H2O, –H+
O
O
O
H+
N
N
O
N
O
O
OH2
O
OH
H
O
Ar
O
O
O
N
O
N
O
4
Scheme 2.
compared with the carbonyl species is utilized to facilitate
Knoevenagel condensation between arylaldehyde 2 and
1,3-dimethylbarbituric acid 3 via intermediate 5, and after
dehydration olefin 6 is produced. Subsequent Michael-
type addition of 1 to the olefin followed by cyclization
and dehydration affords the corresponding products 4a-4i.
mass spectrometer (Waters) by electro-spray method
(ES); melting points were determined on a XT-4 binocular
microscope and were uncorrected; commercially available
reagents were used without further purification.
General procedure for the preparation of 4
Conclusions
A mixture of 3,4-methylenedioxyphenol (1 mmol),
aldehyde (1 mmol), 1,3-dimethylbarbituric acid (1 mmol)
and Zr(HSO4)4 (0.1 mmol) was heated at 100 C for an
appropriate time (TLC). After completion, the reaction
mixture was washed with water (15 mL) and the residue
was recrystallized to afford the pure product 4.
o
In conclusion, we have developed a highly efficient
methodology for the three-component reaction of
3,4-methylenedioxyphenol, aromatic aldehydes, and
1,3-dimethylbarbituric acid catalyzed by safe Zr(HSO4)4,
furnishing a class of 10-aryl-6,8-dimethyl-6,10- dihydro-5-
oxa-6,8-diazaanthra[2,3-d][1,3]dioxole-7,9- diones in high
yield. This method is advantageous in terms of simplicity
and mildness, and could find wide application in synthesis
of complex benzo[1,3]dioxole-containing compounds.
10-Phenyl-6,8-dimethyl-6,10-dihydro-5-oxa-6,8-
diazaanthra[2,3-d][1,3]dioxole-7,9-dione (4a)
White powder, mp 245-246oC; IR (KBr) νmax/cm-1: 3076,
2972, 2899, 1703, 1667, 1659, 1482, 1432, 1211, 1139, 1031,
929, 878, 826, 745, 702, 572, 517, 421; 1H NMR (CDCl3,
400 MHz) d 7.26-7.16 (m, 5H, ArH), 6.68 (s, 1H,ArH), 6.52
(s, 1H, ArH), 5.95 (d, 1H, J 0.8 Hz, OCH2O), 5.91 (d, 1H,
J 0.8 Hz, OCH2O), 5.03 (s, 1H, CH), 3.55 (s, 3H, CH3),
3.28 (s, 3H, CH3); 13C NMR (CDCl3, 100 MHz) d 161.9,
152.6, 150.7, 147.2, 145.6, 145.1, 143.1, 128.6, 127.8, 127.7,
126.9, 116.8, 108.2, 101.8, 98.0, 90.0, 39.2, 29.0, 28.1; MS
(ESI): m/z 365 [M+H]+;Anal. calc. for C20H16N2O5:C 65.93,
H 4.43, N 7.69; found: C 65.90, H 4.48, N 7.74.
Experimental
IR spectra were determined on a FTS-40 infrared
spectrometer; NMR spectra were determined on a Bruker
AV-400 instrument at room temperature using TMS as
internal standard; coupling constants (J) were measured
in Hz. Elemental analysis were performed by a Vario-III
elemental analyzer; mass spectra were taken on a Macro

Vol. 22, No. 7, 2011
Zhang et al.
1239
10-(4-Chlorophenyl)-6,8-dimethyl-6,10-dihydro-5-oxa-6,8-
diazaanthra[2,3-d][1,3]dioxole-7,9-dione (4b)
423; 1H NMR (CDCl3, 400 MHz) d 8.12 (d, 2H, J 8.8 Hz,
ArH), 7.43 (d, 2H, J 8.4 Hz, ArH), 6.71 (s, 1H, ArH), 6.44
(s, 1H, ArH), 5.98 (d, 1H, J 0.8 Hz, OCH2O), 5.95 (d, 1H,
J 0.8 Hz, OCH2O), 5.15 (s, 1H, CH), 3.56 (s, 3H, CH3),
3.27 (s, 3H, CH3); 13C NMR (CDCl3, 100 MHz) d 161.8,
152.8, 152.1, 150.5, 147.8, 146.8, 145.9, 143.1, 128.9,
123.9, 114.9, 107.9, 102.1, 98.3, 88.8, 39.1, 29.1, 28.1;
MS (ESI): m/z 410 [M+H]+; Anal. calc. for C20H15N3O7:
C 58.68, H 3.69, N 10.27; found: C 58.60, H 3.72, N 10.20.
White powder, mp 254-255 oC; IR (KBr) νmax/cm-1:
3089, 2958, 2872, 1701, 1667, 1660, 1478, 1434, 1214,
1142, 1088, 1036, 1015, 975, 934, 854, 772, 751, 571, 521,
421; 1H NMR (CDCl3, 400 MHz) d 7.22 (d, 2H, J 6.4 Hz,
ArH), 7.18 (d, 2H, J 6.8 Hz, ArH), 6.67 (s, 1H, ArH), 6.47
(s, 1H,ArH), 5.97 (d, 1H, J 0.8 Hz, OCH2O), 5.92 (d, 1H, J
0.8 Hz, OCH2O), 5.00 (s, 1H, CH), 3.54 (s, 3H, CH3), 3.28
(s, 3H, CH3); 13C NMR (CDCl3, 100 MHz) d 161.8, 152.6,
150.6, 147.4, 145.7, 143.6, 143.0, 132.7, 129.3, 128.8,
128.7, 116.1, 108.0, 101.9, 98.1, 89.6, 38.6, 29.0, 28.1;
MS (ESI): m/z 399 [M+H]+; Anal. calc. for C20H15ClN2O5:
C 60.23, H 3.79, N 8.89; found: C 60.19, H 3.85, N 8.95.
10-(3-Nitrophenyl)-6,8-dimethyl-6,10-dihydro-5-oxa-6,8-
diazaanthra[2,3-d][1,3]dioxole-7,9-dione (4f)
White powder, mp 262-263 oC; IR (KBr) νmax/cm-1:
3052, 2944, 2852, 1701, 1666, 1659, 1529, 1504, 1486,
1436, 1351, 1224, 1171, 1038, 934, 871, 737, 717; 1H NMR
(CDCl3, 400 MHz) d 8.05-8.03 (m, 1H, ArH), 8.00-7.98
(m, 1H, ArH), 7.72 (d, 1H, J 7.6 Hz, ArH), 7.46 (t, 1H,
J 7.6 Hz, ArH), 6.71 (s, 1H, ArH), 6.44 (s, 1H, ArH),
5.98 (d, 1H, J 0.8 Hz, OCH2O), 5.94 (d, 1H, J 0.8 Hz,
OCH2O), 5.15 (s, 1H, CH), 3.57 (s, 3H, CH3), 3.27 (s,
3H, CH3); 13C NMR (CDCl3, 100 MHz) d 161.8, 152.8,
150.5, 148.5, 147.8, 147.1, 145.9, 143.0, 134.5, 129.3,
122.9, 115.0, 107.9, 102.1, 98.4, 88.8, 39.1, 29.1, 28.1;
MS (ESI): m/z 410 [M+H]+; Anal. calc. for C20H15N3O7:
C 58.68, H 3.69, N 10.27; found: C 58.72, H 3.75, N 10.22.
10-(4-Fluorophenyl)-6,8-dimethyl-6,10-dihydro-5-oxa-6,8-
diazaanthra[2,3-d][1,3]dioxole-7,9-dione (4c)
White powder, mp 253-254 oC; IR (KBr) νmax/cm-1:
3079, 2962, 2859, 1707, 1667, 1648, 1522, 1436, 1353,
1212, 1142, 1031, 977, 930, 864, 817, 751, 703, 570, 516,
1
422; H NMR (CDCl3, 400 MHz) d 7.22-7.19 (m, 2H,
ArH), 6.95-6.91 (m, 2H, ArH), 6.67 (s, 1H, ArH), 6.48 (s,
1H, ArH), 5.96 (d, 1H, J 1.2 Hz, OCH2O), 5.92 (d, 1H,
J 1.2 Hz, OCH2O), 5.01 (s, 1H, CH), 3.54 (s, 3H, CH3),
3.28 (s, 3H, CH3); 13C NMR (CDCl3, 100 MHz) d 161.9,
152.5, 150.6, 147.3, 145.6, 143.0, 140.9, 129.4, 116.5,
115.4, 115.2, 108.1, 101.9, 98.0, 89.8, 38.4, 29.0, 28.1;
MS (ESI): m/z 383 [M+H]+; Anal. calc. for C20H15FN2O5:
C 62.83, H 3.95, N 7.33; found: C 62.90, H 3.89, N 7.40.
10-(3,4-Dichlorophenyl)-6,8-dimethyl-6,10-dihydro-5-oxa-
6,8-diazaanthra[2,3-d][1,3]dioxole-7,9-dione (4g)
o
White powder, mp 247-248 C; IR (KBr) νmax/cm-1:
3092, 2972, 2861, 1682, 1588, 1561, 1426, 1383, 1318,
1
10-(4-Methylphenyl)-6,8-dimethyl-6,10-dihydro-5-oxa-6,8-
diazaanthra[2,3-d][1,3]dioxole-7,9-dione (4d)
1250, 1112, 1036, 934, 868, 762, 562; H NMR (CDCl3,
400 MHz) d 7.33 (d, 1H, J 8.0 Hz, ArH), 7.26-7.25 (m,
1H, ArH), 7.15 (dd, 1H, J 2.0, 8.0 Hz, ArH), 6.68 (s, 1H,
ArH), 6.45 (s, 1H, ArH), 5.98 (d, 1H, J 0.8 Hz, OCH2O),
5.94 (d, 1H, J 0.8 Hz, OCH2O), 4.98 (s, 1H, CH), 3.55 (s,
3H, CH3), 3.28 (s, 3H, CH3); 13C NMR (CDCl3, 100 MHz)
d 161.8, 152.7, 150.6, 147.6, 145.8, 145.3, 143.0, 132.6,
131.0, 130.4, 129.8, 127.5, 115.4, 107.9, 102.0, 98.2, 89.0,
38.5, 29.1, 28.1; MS (ESI): m/z 433 [M+H]+;Anal. calc. for
C20H14Cl2N3O7: C 55.45, H 3.26, N 6.47; found: C 55.50,
H 3.20, N 6.50.
White powder, mp 248-249 oC; IR (KBr) νmax/cm-1:
3078, 2956, 2870, 1708, 1671, 1644, 1478, 1434, 1211,
1140, 1032, 930, 930, 790, 572, 519, 421; 1H NMR (CDCl3,
400 MHz) d 7.14 (d, 2H, J 8.0 Hz, ArH), 7.07 (d, 2H, J
8.0 Hz, ArH), 6.67 (s, 1H, ArH), 6.52 (s, 1H, ArH), 5.95
(d, 1H, J 0.8 Hz, OCH2O), 5.90 (d, 1H, J 0.8 Hz, OCH2O),
4.99 (s, 1H, CH), 3.54 (s, 3H, CH3), 3.28 (s, 3H, CH3),
2.27 (s, 3H, CH3); 13C NMR (CDCl3, 100 MHz) d 161.9,
152.5, 150.7, 147.1, 145.5, 143.0, 142.3, 136.5, 129.3,
129.2, 127.7, 127.6, 117.0, 108.2, 101.8, 98.0, 90.1, 38.8,
29.0, 28.1, 21.0; MS (ESI): m/z 379 [M+H]+; Anal. calc.
for C21H18N2O5:C 66.66, H 4.79, N 7.40; found: C 66.70,
H 4.69, N 7.49.
10-(2,4-Dichlorophenyl)-6,8-dimethyl-6,10-dihydro-5-oxa-
6,8-diazaanthra[2,3-d][1,3]dioxole-7,9-dione (4h)
White powder, mp 277-278 C; IR (KBr) νmax/cm-1:
o
3082, 2979, 2870, 1700, 1667, 1641, 1480, 1433, 1395,
1
10-(4-Nitrophenyl)-6,8-dimethyl-6,10-dihydro-5-oxa-6,8-
diazaanthra[2,3-d][1,3]dioxole-7,9-dione (4e)
White powder, mp 259-260 oC; IR (KBr) νmax/cm-1:
3089, 2991, 2881, 1706, 1668, 1650, 1522, 1437, 1395,
1352, 1213, 1143, 1032, 978, 929, 863, 816, 752, 570, 517,
1219, 1148, 1037, 934, 878, 794, 755, 594; H NMR
(CDCl3, 400 MHz) d 7.36 (d, 1H, J 2.0 Hz, ArH), 7.14-
7.12 (m, 2H, ArH), 6.63 (s, 1H, ArH), 6.55 (s, 1H, ArH),
5.96 (d, 1H, J 1.6 Hz, OCH2O), 5.92 (d, 1H, J 1.6 Hz,
OCH2O), 5.52 (s, 1H, CH), 3.57 (s, 3H, CH3), 3.27 (s, 3H,

1240
Zr(HSO4)4 as an Efficient Catalyst for a solvent free one-pot three-component condensation
J. Braz. Chem. Soc.
CH3); 13C NMR (CDCl3, 100 MHz) d 161.7, 153.1, 150.7,
147.4, 145.6, 142.7, 141.0, 133.5, 133.2, 131.2, 129.7,
127.6, 115.1, 107.5, 101.9, 98.0, 88.2, 38.6, 29.1, 28.1;
MS (ESI): m/z 433 [M+H]+;Anal. calc. for C20H14Cl2N3O7:
C 55.45, H 3.26, N 6.47; found: C 55.38, H 3.24, N 6.52.
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10-(2-Chlorophenyl)-6,8-dimethyl-6,10-dihydro-5-oxa-6,8-
diazaanthra[2,3-d][1,3]dioxole-7,9-dione (4i)
o
White powder, mp 233-234 C; IR (KBr) νmax/cm-1:
6. Burguete, A.; Pontiki, E.; Hadjipavlou-Litina, D.; Villar, R.; E.
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8. Liu, Y.-Q.; Yang, L.; Tian, X.; Curr. Bioact. Compd. 2007, 3,
37.
3082, 2965, 2858, 1701, 1663, 1520, 1435, 1361, 1281,
1
1118, 1036, 936, 736, 427; H NMR (CDCl3, 400 MHz)
d 7.34 (d, 1H, J 7.6 Hz, ArH), 7.17-7.12 (m, 3H, ArH),
6.63 (s, 1H, ArH), 6.61 (s, 1H, ArH), 5.95 (d, 1H, J 0.8 Hz,
OCH2O), 5.90 (d, 1H, J 0.8 Hz, OCH2O), 5.58 (s, 1H, CH),
3.57 (s, 3H, CH3), 3.27 (s, 3H, CH3); 13C NMR (CDCl3,
100 MHz) d161.7, 153.1, 150.8, 147.3, 145.5, 142.7, 142.3,
132.8, 130.3, 130.0, 128.1, 127.2, 115.7, 107.7, 101.8, 97.9,
88.7, 38.2, 29.1, 28.1; MS (ESI): m/z 399 [M+H]+; Anal.
calc. for C20H15ClN2O5:C 60.23, H 3.79, N 8.89; found: C
60.22, H 3.80, N 8.92.
9. Shamroukh, A. H.; Zaki, M. E. A.; Morsy, E. M. H.; Abdel-
Motti, F. M.;Abdel-Megeid, F. M. E.; Arch. Pharm. 2007, 340,
236.
10. Mostafa, M. S.; J. Environ. Sci. 2008, 36, 255; Eid, F. A.; Abd
El-Wahab, A. H. F.; El-Hag Ali, G. A. M.; Khafagy, M. M.;
Acta Pharm. 2004, 54, 13; Bedair, A. H.; Emam, H. A.;
El-Hady, N. A.; Ahmed, K. A. R.; El-Agrody, A. M.; Farmaco
2001, 56, 965; Ahluwalia, V. K.; Chopra, M.; Chandra, R.;
J. Chem. Res. (S) 2000, 162.
Supplementary Information
1
The spectroscopic H NMR, 13C NMR, and IR data
of 4a-4i are provided as supplementary information and
available free of charge at http://jbcs.sbq.org.br as PDF file.
11. Akluwalia,V. K.; Bala, M.; Indian J. Chem., Sect. B 1996, 35B,
742.
12. Joshi, K. C.; Jain, R.; Sharma, K.; Bhattacharya, S. K.; Goel,
R. K.; J. Indian Chem. Soc. 1988, 65, 202.
Acknowledgments
13. Yoneda, F.; Hirayama, R.; Yamashita, M.; Chem. Lett. 1980,
1157; Chen, X.; Tanaka, K.; Yoneda, F.; Chem. Pharm. Bull.
1990, 38, 307.
We are pleased to acknowledge the financial support
from Xinxiang Medical University.
14. Das, B.; Venkataiah, B.; Synthesis 2000, 1671; Ramesh, C.;
Ravindranath, N.; Das, B.; J. Org. Chem. 2003, 68, 7101;
Shirini, F.; Zolfigol, M. A.; Safari, A.; Indian J. Chem., Sect.
B 2005, 44B, 201; Khodaei, M. M.; Salehi, P.; Zolfigol, M.
A.; Sirouszadeh, S.; Polish J. Chem. 2004, 78, 38; Shirini, F.;
Zolfigol, M. A.; Mallakpour, B.; Russ. J. Org. Chem. 2005, 41,
625; Shaabani, A.; Bazgir, A.; Soleimani, K,; Salehi, P.; Synth.
Commun. 2003, 33, 2935; Mirjalili, B. F.; Zolfigol, M. A.;
Bamoniri, A.; Karimi-Zarchi, M. A.; Zaghaghi, Z.; Parvaideh,
M.; J. Iran. Chem. Soc. 2007, 4, 340; Shaabani, A.; Zolfigol,
M. A.; Abedini, M.; Bull. Chem. Soc. Jpn. 2005, 78, 1982.
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Submitted: October 25, 2010
Published online: February 24, 2011

J. Braz. Chem. Soc., Vol. 22, No. 7, S1-S14, 2011.
Printed in Brazil - ©2011 Sociedade Brasileira de Química
0103 - 5053 $6.00+0.00
Supplementary Information
SI
Zr(HSO4)4 as an Efficient Catalyst for the Preparation of 10-Aryl-6,8-dimethyl-6,10-
dihydro-5-oxa-6,8-diazaanthra[2,3-d][1,3]dioxole-7,9-diones under
Solvent-Free Conditions
Jiangli Zhang,a Wei Lin Lib and Li Qiang Wu*,b
aThe Department Psychology of the Second Affiliated, Xinxiang Medical University,
453000 Xinxiang, Henan, P. R. China
bSchool of Pharmacy, Xinxiang Medical University, 453000 Xinxiang, Henan, P. R. China
Figure S1. IR (KBr) of 4a.
*e-mail: wliq870@163.com

S2
Zr(HSO4)4 as an Efficient Catalyst for a solvent free one-pot three-component condensation
J. Braz. Chem. Soc.
Figure S2. 1H NMR of 4a (400 MHz, CDCl3).
Figure S3. 13C NMR of 4a (100 MHz, CDCl3).

Vol. 22, No. 7, 2011
Zhang et al.
S3
Figure S4. IR (KBr) of 4b.
Figure S5. 1H NMR of 4b (400 MHz, CDCl3).

S4
Zr(HSO4)4 as an Efficient Catalyst for a solvent free one-pot three-component condensation
J. Braz. Chem. Soc.
Figure S6. 13C NMR of 4b (100 MHz, CDCl3).
Figure S7. IR (KBr) of 4c.

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Zhang et al.
S5
Figure S8. 1H NMR of 4c (400 MHz, CDCl3).
Figure S9. 13C NMR of 4c (100 MHz, CDCl3).

S6
Zr(HSO4)4 as an Efficient Catalyst for a solvent free one-pot three-component condensation
J. Braz. Chem. Soc.
Figure S10. IR (KBr) of 4d.
Figure S11. 1H NMR of 4d (400 MHz, CDCl3).

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Zhang et al.
S7
Figure S12. 13C NMR of 4d (100 MHz, CDCl3).
Figure S13 IR (KBr) of 4e.

S8
Zr(HSO4)4 as an Efficient Catalyst for a solvent free one-pot three-component condensation
J. Braz. Chem. Soc.
Figure S14. 1H NMR of 4e (400 MHz, CDCl3).
Figure S15. 13C NMR of 4e (100 MHz, CDCl3).

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Zhang et al.
S9
Figure S16. IR (KBr) of 4f.
Figure S17. 1H NMR of 4f (400 MHz, CDCl3).

S10
Zr(HSO4)4 as an Efficient Catalyst for a solvent free one-pot three-component condensation
J. Braz. Chem. Soc.
Figure S18. 13C NMR of 4f (100 MHz, CDCl3).
Figure S19. IR (KBr) of 4g.

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Zhang et al.
S11
Figure S20. 1H NMR of 4g (400 MHz, CDCl3).
Figure S21. 13C NMR of 4g (100 MHz, CDCl3).

S12
Zr(HSO4)4 as an Efficient Catalyst for a solvent free one-pot three-component condensation
J. Braz. Chem. Soc.
Figure S22. IR (KBr) of 4h.
Figure S23. 1H NMR of 4h (400 MHz, CDCl3).

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Zhang et al.
S13
Figure S24. 13C NMR of 4h (100 MHz, CDCl3).
Figure S25. IR (KBr) of 4i.

S14
Zr(HSO4)4 as an Efficient Catalyst for a solvent free one-pot three-component condensation
J. Braz. Chem. Soc.
Figure S26. 1H NMR of 4i (400 MHz, CDCl3).
Figure S27. 13C NMR of 4i (100 MHz, CDCl3).