Green synthesis of 3-hydroxynaphthalene-1,4-dione derivatives via microwave-assisted three-component reactions in neat water

Article abstract of DOI:10.1002/jhet.798

A novel and efficient access to 2-(argio(3-methyl-5-oxo-1-phenyl-4,5- dihydro-1H-pyrazol-4-yl)methyl)-3-hydroxynaphthalene-1,4-dione derivatives from readily available substrates in neat water is described with aid of microwave irradiation. The results of our study provide a green, simple and practical one-pot approach to the synthesis of 3-hydroxynaphthalene-1,4-dione analogs in excellent yields without further purification.

Full text of DOI:10.1002/jhet.798

May 2012
Green Synthesis of 3-Hydroxynaphthalene-1,4-dione Derivatives
via Microwave-Assisted Three-Component Reactions
in Neat Water
521
Shu-Liang Wang, Jie Ding, Fen Shi, Yin-Ping Liu, Bo Jiang,
*
Ning Ma, and Shu-Jiang Tu
School of Chemistry and Chemical Engineering, Xuzhou Normal University, Xuzhou,
Jiangsu 221116, People’s Republic of China
*
E-mail: laotu2001@263.net
Received September 15, 2010
DOI 10.1002/jhet.798
View this article online at wileyonlinelibrary.com.
A novel and efficient access to 2-(argio(3-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazol-4-yl)
methyl)-3-hydroxynaphthalene-1,4-dione derivatives from readily available substrates in neat water is de-
scribed with aid of microwave irradiation. The results of our study provide a green, simple and practical
one-pot approach to the synthesis of 3-hydroxynaphthalene-1,4-dione analogs in excellent yields with-
out further purification.
J. Heterocyclic Chem., 49, 521 (2012).
INTRODUCTION
ynaphthalene-1,4-diones, imbedded with the two motifs of
pyrazole and NQ, has seldom been reported. To expand the
families containing NQ skeletons, the development of
practically simple, economical, and environmentally
friendly routes to a wide variety of 3-hydroxynaphthalene-
1,4-dione derivatives is strongly desired.
Water, a safe and environmentally benign solvent, has
attracted much attention in synthetic chemistry recently
[16]. The both use of water as solvent and microwave
(MW) irradiation for heating make the reaction process
more attractive as it combines the two prominent green
chemistry principles of “safer solvents” and “energy
efficiency” [17].
In view of the prominent merits of MW-assisted
multicomponent reactions in water and as a continuation
of our efforts on synthesizing bioactive heterocyclic
compounds with green approach [18], herein, we report
a green method to prepare a new class of NQ deriva-
tives 4 integrated with pyrazole unit by MW-assisted
three-component condensations of 2-hydroxynaphtha-
lene-1,4-dione 1, aldehyde 2, and 3-methyl-1-phenyl-
1H-pyrazol-5(4H)-one 3 in water (Scheme 1).
Naphthoquinones (NQs) are compounds present in the
secondary metabolites of plants and microorganisms,
which confer activity in various biological oxidative pro-
cesses. Originating among native Ameridian populations,
plants containing NQs have been used for the treatment of
a number of diseases such as cancer [1,2]. Mass screening
programs of natural products by the National Cancer Insti-
tute have identified the quinone moiety as an important
pharmacophoric element for cytotoxic activity [3].
Furthermore, the NQ subunit is considered as privileged
structures in medicinal chemistry [4] with numerous bioac-
tivities [5] including antibacterial [6], fungicidal [6], anti-
malarial [7], trypanocidal [8], and antitumoral [9] activities.
Pyrazoles are of interest as possible antiviral agents [10]
and a wide spectrum of pharmacological activities are
described for them, exemplified by antimalarial [11],
immunostimulatory [12], antianginal [13], and antitumor
[14] properties. Based on the versatile bioactivities of pyr-
azoles and NQs, it is promising that the integration of
these two bioactive units into an organic whole may ex-
hibit new or improved pharmacological properties.
Recently, we have synthesized a new class of a-lapa-
chone derivatives with diverse structures in one pot by
three-component condensations [15]. However, to the best
of our knowledge, the synthesis of 2-(argio(3-methyl-5-
oxo-1-phenyl-4,5-dihydro-1H-pyrazol-4-yl)methyl)-3-hydrox-
RESULTS AND DISCUSSION
To choose the most appropriate solvent, the MW-assisted
reaction (Scheme 2) of 2-hydroxynaphthalene-1,4-dione
(1, 1.0 mmol), 4-chlorobenzaldehyde (2c, 1.0 mmol),
© 2012 HeteroCorporation

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S.-L. Wang, J. Ding, F. Shi, Y.-P. Liu, B. Jiang, N. Ma, and S.-J. Tu
Vol 49
Table 1
Optimization for the synthesis of 4c under microwave irradiation.
Scheme 1
Entry
Solvent Temperature (ꢀC) Time (min) Yield (%)
1
2
3
4
5
6
7
8
10
EtOH
Glycol
DMF
HOAc
Water
Water
Water
Water
Water
120
120
120
120
100
110
120
130
140
6
6
6
6
6
6
6
6
6
30
45
63
78
59
72
88
82
69
and 3-methyl-1-phenyl-1H-pyrazol-5(4H)-one (3, 1.0 mmol)
was examined using ethanol (EtOH), ethylene glycol,
N,N-dimethylformamide (DMF), glacial acetic acid
(HOAc), and water as the solvent (2.0 mL) at 120ꢀC,
respectively. All the reactions were carried out at the
maximum power of 250 W (initial power 100 W). Reac-
tion under EtOH and ethylene glycol, afforded the product
with very low yield (less than 45%).
The use of DMF gave rise to side reactions and therefore
led to low product yields (63%). As shown in Table 1,
the reaction with HOAc and H2O both gave higher
yields. Although the reaction in HOAc proceeded with
better yield than that in H2O, finally water was used
as the reaction media for the following reactions, be-
cause it turned out to be the best choice in view of its
relatively environmental-friendly characteristics, as a
“cleaner” reaction medium compared with others
(Table 1, entries 1–4).
To further optimize reaction conditions, the same reac-
tion was performed in water and 250 W at tempera-
tures ranging from 100 to 140ꢀC. Initially, the product
4c was easily obtained with yield 59% (100ꢀC). The
yield of product 4c was increased as the temperature
was increased from 100 to 120ꢀC (Table 1, entries 5–7).
However, further increase of the temperature from 130
to 140ꢀC (Table 1, entries 9 and 10) failed to improve
the yield of 4c. Therefore, 120ꢀC was chosen as the re-
action temperature for all further MW-assisted reac-
tions (Scheme 1).
as alkoxy) readily provided compounds 4 in good yields
(Table 2, entries 1–12). Moreover, heterocyclic aldehydes
such as thiophene-2-carbaldehyde (Table 2, entry 13) still
displayed a high reactivity under this standard condi-
tion. It is worth noting that this conclusion is significant
since there is no literature precedent for the synthesis of
3-hydroxynaphthalene-1,4-diones.
The formation of 4 is expected to proceed via initial
condensation of aldehydes with 2-hydroxynaphthalene-
1,4-dione to afford 3-(argiomethylene)naphthalene-
1,2,4(3H)-trione 5, which further undergoes in situ
Michael addition with 3-methyl-1-phenyl-1H-pyrazol-
5-ol 6, isomerized by 3-methyl-1-phenyl-1H-pyrazol-
5(4H)-one 3, to yield final product 4 (Scheme 3). In this
study, all the products were characterized by IR, 1H-NMR,
and MS. Furthermore, the structure of 4d was established
by X-ray crystallography [19]. The molecular structure
of 4d was shown in Figure 1.
In summary, we demonstrated a rapid and direct route
for the one-pot green synthesis of 2-(argio(3-methyl-5-
oxo-1-phenyl-4,5-dihydro-1H-pyrazol-4-yl)methyl)-3-hydro-
xynaphthalene-1,4-diones from easily available substrates
in aqueous medium. Particularly, valuable features of this
method included environmental friendliness, operational
simplicity, short reaction time, high yields, and broader
substrate scope.
Under the optimal conditions [H2O, 120ꢀC, 250 W
(maximum power)], reactions of different aldehydes
were performed and afforded various 3-hydroxynaphtha-
lene-1,4-diones. As shown in Table 2, we made a
research for the aldehyde substrate scope, and the results
indicated that aromatic aldehydes bearing both electron-
withdrawing (such as nitro) and electron-donating (such
EXPERIMENTAL
All reactions were performed in a monomodal EmrysTM
Creator from Personal Chemistry, Uppsala, Sweden. Melting
points were determined in open capillaries and are uncorrected.
IR spectra were recorded on a FT-IR-tensor 27 spectrometer in
KBr. 1H-NMR spectra were measured on a DPX 400 MHz
spectrometer using TMS as an internal standard and DMSO-d6
as solvent. HRMS (ESI) was determined by using the micrO-
TOF-Q II HPLC/MS instrument (BRUKER). X-Ray crystallo-
graphic analysis was performed with a Siemens SMART CCD
and a Semens P4 diffractometer.
Scheme 2
Sample experimental. General procedure for the synthe-
sis of 3-hydroxynaphthalene-1,4-dione derivatives 4 under
microwave irradiation. In a 10-mL EmrysTM reaction vial,
2-hydroxynaphthalene-1,4-dione (1 mmol) with aromatic
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

May 2012
Green Synthesis of 3-Hydroxynaphthalene-1,4-dione Derivatives via Microwave-Assisted
523
Three-Component Reactions in Neat Water
Table 2
The synthesis of compounds 4.
Entry
Compound
Ar
Time (min)
Yield (%)
Mp (ꢀC)
1
2
3
4
5
6
7
8
4a
4b
4c
4d
4e
4f
4g
4h
4i
C6H5
4-FC6H4
7
6
6
8
7
5
7
7
9
7
7
9
8
85
79
88
86
90
82
77
89
77
82
78
84
72
267.2–268.4
257.5–259.6
262.1–264.0
257.3–258.5
270.0–271.8
247.3–248.9
266.2–268.0
265.3–266.4
235.3–237.4
261.7–263.2
211.3–212.6
257.2–259.5
238.7–239.8
4-ClC6H4
2,4-Cl2C6H4
4-BrC6H4
4-O2NC6H4
3-O2NC6H4
4-MeC6H4
3,4-(MeO)2C6H3
3,4-OCH2OC6H3
4-Me2NC6H4
9
10
11
12
13
4j
4k
4l
4-Benzo[d]oxazol-2-yl
Thiophen-2-yl
4m
aldehyde (1.0 mmol) and 3-methyl-1-phenyl-1H-pyrazol-
5(4H)-one (1.0 mmol) and water (2.0 mL) were mixed and
then capped. The mixture was irradiated by MW at 250 W and
120ꢀC for a given time. The automatic mode stirring helped
the mixing and uniform heating of the reactants. Upon comple-
tion, monitored by thin layer chromatography (TLC), the
reaction mixture was cooled to room temperature and then
poured into cold water, filtered to give the crude products,
which were further purified by recrystallization from 95%
EtOH. The reaction time and the yields are listed in Table 2.
The analytical data of new products are as following.
CH3). HRMS (ESI): m/z [M + Na]+ calcd. for C29H21FO4:
477.1222; found: 477.1216.
2-((4-Chlorophenyl)(3-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-
pyrazol-4-yl)methyl)-3-hydroxynaphthalene-1,4-dione (4c).
(KBr): 3155, 3058, 1659, 1633, 1605, 1572, 1500, 1488, 1376,
1287, 1094, 955, 823, 726, 612 cmÀ1 1H-NMR (400 MHz,
IR
.
DMSO) (d, ppm): 8.03 (d, J = 7.6 Hz, 1H, ArH), 7.97 (d, J = 7.6 Hz,
1H, ArH), 7.85–7.76 (m, 2H, ArH), 7.69 (d, J = 8.0 Hz,
2H, ArH), 7.49 (t, J = 8.0 Hz, 2H, ArH), 7.32–7.24 (m, 5H,
ArH), 5.81 (s, 1H, CH), 2.28 (s, 3H, CH3). HRMS (ESI): m/z
[M + Na]+ calcd. for C27H19ClN2O4: 493.0926; found:
493.0916.
2-Hydroxy-3-((3-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazol-
4-yl)(phenyl)methyl)naphthalene-1,4-dione (4a). IR (KBr): 3175,
3069, 1656, 1634, 1605, 1572, 1501, 1460, 1375, 1287, 1122,
2-((2,4-Dichlorophenyl)(3-methyl-5-oxo-1-phenyl-4,5-dihydro-
1H-pyrazol-4-yl)methyl)-3-hydroxynaphthalene-1,4-dione (4d). IR
(KBr): 3174, 3067, 1648, 1609, 1593, 1577, 1502, 1468, 1373,
1030, 954, 833, 728, 695, 610 cmÀ1 1H-NMR (400 MHz,
.
DMSO) (d, ppm): 8.04 (d, J = 6.8 Hz, 1H, ArH), 7.97 (d, J = 6.4 Hz,
1H, ArH), 7.84–7.77 (m, 2H, ArH), 7.69 (d, J = 6.4 Hz, 2H, ArH),
7.51–7.47 (m, 2H, ArH), 7.32–7.18 (m, 6H, ArH), 5.85 (s, 1H, CH),
2.27 (s, 3H, CH3). HRMS (ESI): m/z [M + Na]+ calcd. for
C27H20N2O4: 459.1316; found: 459.1329.
1256, 1119, 1047, 955, 838, 753 cmÀ1 1H-NMR (400 MHz,
.
DMSO) (d, ppm): 7.99 (t, J = 7.8 Hz, 2H, ArH), 7.86–7.76
(m, 2H, ArH), 7.71 (d, J = 7.6 Hz, 2H, ArH), 7.54 (s, 1H, ArH),
7.48–7.43 (m, 3H, ArH), 7.37 (dd, J1 = 8.4 Hz, J2 = 2.0 Hz,
1H, ArH), 7.25 (t, J = 7.2 Hz, 1H, ArH), 5.76 (s, 1H, CH),
2-((4-Fluorophenyl)(3-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-
pyrazol-4-yl)methyl)-3-hydroxynaphthalene-1,4-dione (4b). IR
(KBr): 3174, 3067, 1656, 1634, 1608, 1571, 1504, 1376, 1254,
1157, 1016, 956, 823, 729, 615 cmÀ1. 1H-NMR (400 MHz, DMSO)
(d, ppm): 8.04 (d, J = 7.6 Hz, 1H, ArH), 7.97 (d, J = 7.2 Hz,
1H, ArH), 7.85–7.76 (m, 2H, ArH), 7.69 (d, J = 7.6 Hz, 2H,
ArH), 7.49 (t, J = 8.0 Hz, 2H, ArH), 7.32–7.24 (m, 3H, ArH),
7.08 (t, J = 8.8 Hz, 2H, ArH), 5.81 (s, 1H, CH), 2.27 (s, 3H,
Scheme 3
Figure 1. ORTEP diagram of 4d.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

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S.-L. Wang, J. Ding, F. Shi, Y.-P. Liu, B. Jiang, N. Ma, and S.-J. Tu
Vol 49
2.08 (s, 3H, CH3). HRMS (ESI): m/z [M + Na]+ calcd. for
C27H18Cl2N2O4: 527.0536; found: 527.0553.
5.96 (s, 2H, CH2), 5.74 (s, 1H, CH), 2.26 (s, 3H, CH3). HRMS
(ESI): m/z [M + Na]+ calcd. for C28H20N2O6: 503.1214; found:
503.1203.
2-((4-(Bimethylamino)phenyl)(3-methyl-5-oxo-1-phenyl-4,5-
dihydro-1H-pyrazol-4-yl)methyl)-3-hydroxynaphthalene-1,4-dione
2-((4-Bromophenyl)(3-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-
pyrazol-4-yl)methyl)-3-hydroxynaphthalene-1,4-dione (4e). IR (KBr):
3149, 3055, 1660, 1633, 1605, 1572, 1500, 1484, 1373, 1285, 1252,
1
1074, 1010, 955, 821, 757 cmÀ1. H-NMR (400 MHz, DMSO)
(4k).
1606, 1573, 1520, 1499, 1361, 1280, 1164, 1066, 953, 812,
756, 727, 694 cmÀ1 1H-NMR (400 MHz, DMSO) (d, ppm):
IR (KBr): 3150, 3096, 3010, 2963, 2808, 1653, 1638,
(d, ppm): 8.03 (d, J = 7.6 Hz, 1H, ArH), 7.97 (d, J = 7.6 Hz,
1H, ArH), 7.85–7.76 (m, 2H, ArH), 7.70 (d, J = 8.0 Hz, 2H,
ArH), 7.51–7.43 (m, 4H, ArH), 7.30 (t, J = 7.2 Hz, 1H, ArH),
7.19 (d, J = 8.0 Hz, 2H, ArH), 5.79 (s, 1H, CH), 2.28 (s, 3H,
CH3). HRMS (ESI): m/z [M + Na]+ calcd. for C27H19BrN2O4:
537.0421; found: 537.0431.
.
8.02 (d, J = 7.2 Hz, 1H, ArH), 7.95 (d, J = 7.6 Hz, 1H,
ArH), 7.84–7.74 (m, 2H, ArH), 7.70 (d, J = 8.0 Hz, 2H,
ArH), 7.48 (t, J = 8.0 Hz, 2H, ArH), 7.28 (t, J = 7.2 Hz,
1H, ArH), 7.06 (d, J = 8.4 Hz, 2H, ArH), 6.74–6.72 (m, 2H,
ArH), 5.74 (s, 1H, CH), 2.87 (s, 6H, 2CH3), 2.25 (s, 3H,
CH3). HRMS (ESI): m/z [M + Na]+ calcd. for C29H25N3O4:
502.1738; found: 502.1715.
2-Hydroxy-3-((3-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazol-
4-yl)(4-nitrophenyl)methyl)naphthalene-1,4-dione (4f). IR (KBr):
3154, 3072, 2903, 1672, 1639, 1604, 1575, 1459, 1346, 1253,
954, 851, 728, 692 cmÀ1
.
1H-NMR (400 MHz, DMSO) (d,
2-((4-(Benzo[d]oxazol-2-yl)phenyl)(3-methyl-5-oxo-1-phenyl-
4,5-dihydro-1H-pyrazol-4-yl)methyl)-3-hydroxynaphthalene-1,4-
ppm): 8.12 (d, J = 8.8 Hz, 2H, ArH), 8.04 (d, J = 7.6 Hz, 1,
ArH), 7.98 (d, J = 7.6 Hz, 1H, ArH), 7.86–7.76 (m, 2H,
ArH), 7.70 (d, J = 7.6 Hz, 2H, ArH), 7.50 (q, J = 8.0 Hz,
4H, ArH), 7.30 (t, J = 7.2 Hz, 1H, ArH), 5.91 (s, 1H, CH),
2.28 (s, 3H, CH3). HRMS (ESI): m/z [M + Na]+ calcd. for
dione (4l).
IR (KBr): 3156, 3065, 2967, 1654, 1638, 1609,
1572, 1498, 1453, 1372, 1243, 1061, 953, 808, 760, 727 cmÀ1
.
1H-NMR (400 MHz, DMSO) (d, ppm): 8.11 (d, J = 8.4 Hz,
2H, ArH), 8.06 (d, J = 7.6 Hz, 1H, ArH), 7.99 (d, J = 7.6
Hz, 1H, ArH), 7.85 (t, J = 7.2 Hz, 1H, ArH), 7.82–7.77 (m,
3H, ArH), 7.72 (d, J = 8.0 Hz, 2H, ArH), 7.52–7.47 (m, 4H,
ArH), 7.42–7.39 (m, 2H, ArH), 7.31 (t, J = 7.2 Hz, 1H, ArH),
5.93 (s, 1H, CH), 2.31 (s, 3H, CH3). HRMS (ESI): m/z [M + Na]+
calcd. for C34H23N3O5: 576.1530; found: 576.1523.
C
27H19N3O6: 504.1167; found: 504.1167.
2-Hydroxy-3-((3-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazol-
4-yl)(3-nitrophenyl)methyl)naphthalene-1,4-dione (4g). IR (KBr):
3203, 3071, 3041 1666, 1639, 1608, 1524, 1500, 1460, 1347,
1254, 1123, 964, 861, 726, 687 cmÀ1 1H-NMR (400 MHz,
.
DMSO) (d, ppm): 8.09–8.07 (m, 1H, ArH), 8.05–8.03 (m, 2H,
ArH), 7.98 (d, J = 8.0 Hz, 1H, ArH), 7.86–7.79 (m, 2H,
ArH), 7.76 (d, J = 8.0 Hz, 1H, ArH), 7.70 (d, J = 7.6 Hz,
2H, ArH), 7.57 (t, J = 8.0 Hz, 1H, ArH), 7.50 (t, J = 8.0 Hz,
2H, ArH), 7.31 (t, J = 7.2 Hz, 1H, ArH), 5.93 (s, 1H, CH),
2.29 (s, 3H, CH3). HRMS (ESI): m/z [M + Na]+ calcd. for
C27H19N3O6: 504.1167; found: 504.1166.
2-Hydroxy-3-((3-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazol-
4-yl)(thiophen-2-yl)methyl)naphthalene-1,4-dione (4m). IR (KBr):
3192, 3101, 1657, 1634, 1609, 1571, 1500, 1459, 1375, 1287,
1091, 946, 828, 729, 688, 610 cmÀ1. 1H-NMR (400 MHz, DMSO)
(d, ppm): 8.04 (d, J = 7.6 Hz, 1H, ArH), 7.97 (d, J = 7.6 Hz, 1H,
ArH), 7.86–7.76 (m, 2H, ArH), 7.68 (d, J = 8.4 Hz, 2H, ArH),
7.50 (t, J = 8.0 Hz, 2H, ArH), 7.33–7.30 (m, 2H, ArH), 6.91–6.88
(m, 1H, ArH), 6.85–6.84 (m, 1H, ArH), 5.98 (s, 1H, CH), 2.31 (s,
3H, CH3). HRMS (ESI): m/z [M + H]+ calcd. for C25H18N2O4S:
465.0880; found: 465.0866.
2-Hydroxy-3-((3-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazol-
4-yl)(p-tolyl)methyl)naphthalene-1,4-dione (4h). IR (KBr): 3160,
3057, 1660, 1635, 1604, 1572, 1501, 1459, 1374, 1287, 1254,
954, 814, 753, 730, 691 cmÀ1 1H-NMR (400 MHz, DMSO)
.
(d, ppm): 8.03 (d, J = 7.6 Hz, 1H, ArH), 7.97 (d, J = 7.6 Hz,
1H, ArH), 7.85–7.76 (m, 2H, ArH), 7.70 (d, J = 8.0 Hz, 2H,
ArH), 7.49 (t, J = 8.0 Hz, 2H, ArH), 7.30 (t, J = 7.6 Hz, 1H,
ArH), 7.08 (q, J = 8.0 Hz, 4H, ArH), 5.80 (s, 1H, CH), 2.27
(s, 3H, CH3), 2.25 (s, 3H, CH3). HRMS (ESI): m/z [M + Na]+
calcd. for C28H22N2O4: 473.1472; found: 473.1471.
Acknowledgments. This work was supported by the National
Science Foundation of China (No. 21072163 and 21002083),
Science Foundation in Interdisciplinary Major Research Project of
Xuzhou Normal University (No. 09XKXK01), the Natural Science
Foundation (09KJB150011), and Qing Lan Project (08QLT001) of
Jiangsu Education Committee.
2-((3,4-Dimethoxyphenyl)(3-methyl-5-oxo-1-phenyl-4,5-dihydro-
1H-pyrazol-4-yl)methyl)-3-hydroxynaphthalene-1,4-dione (4i). IR
(KBr): 3158, 3039, 2973, 2834, 1655, 1636, 1604, 1573, 1510,
1460, 1377, 1243, 1143, 1025, 956, 850, 733, 692, 634 cmÀ1
.
1H-NMR (400 MHz, DMSO) (d, ppm): 8.03 (d, J = 6.8 Hz,
1H, ArH), 7.97 (d, J = 7.6 Hz, 1H, ArH), 7.83–7.77 (m, 2H,
ArH), 7.69 (d, J = 7.6 Hz, 2H, ArH), 7.49 (t, J = 8.0 Hz, 2H,
ArH), 7.29 (t, J = 7.2 Hz, 1H, ArH), 6.84–6.73 (m, 3H, ArH),
5.77 (s, 1H, CH), 3.71 (s, 3H, OCH3), 3.62 (s, 3H, OCH3),
2.24 (s, 3H, CH3). HRMS (ESI): m/z [M + H]+ calcd. for
C29H24N2O6: 497.1708; found: 497.1715.
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2-(Benzo[d][1,3]dioxol-5-yl(3-methyl-5-oxo-1-phenyl-4,5-dihydro-
1H-pyrazol-4-yl)methyl)-3-hydroxynaphthalene-1,4-dione (4j). IR
(KBr): 3167, 3064, 2887, 1660, 1639, 1607, 1573, 1501, 1486,
1375, 1238, 1041, 939, 813, 757, 726 cmÀ1. 1H-NMR (400 MHz,
DMSO) (d, ppm): 8.02 (d, J = 7.2 Hz, 1H, ArH), 7.96 (d, J = 7.6 Hz,
1H, ArH), 7.84–7.75 (m, 2H, ArH), 7.69 (d, J = 8.0 Hz, 2H,
ArH), 7.49 (t, J = 8.0 Hz, 2H, ArH), 7.29 (t, J = 7.2 Hz, 1H,
ArH), 6.80–6.78 (m, 2H, ArH), 6.68 (d, J = 8.0 Hz, 1H, ArH),
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Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

May 2012
Green Synthesis of 3-Hydroxynaphthalene-1,4-dione Derivatives via Microwave-Assisted
525
Three-Component Reactions in Neat Water
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[19] The single-crystal growth was carried out in DMF at room
temperature. X-ray crystallographic analysis was performed with a
Siemens SMART CCD and a Semens P4 diffractometer (graphite mono-
chromator, MoKa radiation l = 0.71073 Å). Crystal data for 4d:
Empirical formula C27H17Cl2N2O4, red crystal, crystal dimensions
0.19 mm  0.17 mm  0.06 mm, Monoclinic, space group P2(1)/c,
a = 22.583(2) Å, b = 13.4467(15) Å, c = 15.7624(16) Å, a = 90ꢀ,
b = 97.8920(10)ꢀ, g = 90ꢀ, V = 4741.1(9) Å3, Mr = 504.33, Z = 8,
Dc = 1.413 Mg/m3, l = 0.71073 Å, m (MoKa) = 0.312 mmÀ1, F(000) = 2072,
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Journal of Heterocyclic Chemistry
DOI 10.1002/jhet