J IRAN CHEM SOC
(XRD) pattern was recorded using Philips-1710 diffractom-
pyrazoles were synthesized in high yields (5a–h). The
eter with Cu–Kα radiation (λ = 1.54 A°). The SEM with
EDAX was recorded using JEOL-JEM-6360 microscope.
The TEM was recorded with SAED using CM-200 Philips
microscope. The surface area was recorded with help of
Quantachrome Autosorb Automated Gas Sorption system.
Melting points reported are determined by a melting point
apparatus with open capillary tubes and are uncorrected.
FTIR spectra of different products were recorded on Schi-
catalyst was separated by filtration, dried at 110 °C for 2 h
1
and reused for similar reaction. The spectral data IR, H
1
3
NMR, C NMR and MS of all synthesized compounds are
reported [16–25]. The physical and spectroscopic data of
the synthesized compounds are shown below.
Spectroscopic data
1
−1
madzu 8400s spectrometer using KBr pellets. H NMR
spectra were recorded with a Bruker Advance II 400 MHz
Compound (Table 3, 5a): IR (KBr, cm ): 3,370, 3,307,
1
2,190, 1,609, 1,591, 1,441; H NMR (400 MHz, DMSO-d ,
6
spectrometer in DMSO-d with TMS as an internal stand-
δ): 1.78 (s, 3H, CH ), 4.58 (s, 1H, C-4), 6.85 (s, 2H, NH ),
6
3
2
1
3
13
ard. C NMR spectra were recorded with a Bruker
Advance II 100 MHz spectrometer. Mass spectra were
recorded with a JEOL GCMATE II GC-MS instrument.
7.15–7.33 (m, 5H, Ar–H), 12.08 (s, 1H, NH); C NMR
(100 MHz, DMSO, δ): 9.71, 36.24, 57.15, 97.56, 120.75,
126.67, 127.43, 128.36, 135.51, 144.39, 154.72, 160.82;
+
MF: C H N O; MW: 252; MS (m/z): 253 (M+1) .
1
4
12
4
−1
Typical experimental procedure for the synthesis of ZnS
nanoparticles
Compound (Table 3, 5b): IR (KBr, cm ): 3,381, 3,288,
2,192, 1,626, 1,510, 1,451; H NMR (400 MHz, DMSO-d ,
1
6
δ): 1.81 (s, 3H, CH ), 4.95 (s, 1H, C-4), 6.91 (s, 2H, NH ),
3
2
The ZnS nanoparticles were synthesized by simple hydro-
thermal method using solution of analytical-grade high-
purity zinc nitrate. In the solution of zinc nitrate (10 mmol,
7.40–7.46 (m, 2H, Ar–H), 7.75 (d, 1H, Ar–H, J = 8.40 Hz),
13
7.87 (s, 1H, Ar–H), 12.11 (s, 1H, NH); C NMR
(100 MHz, DMSO, δ): 9.71, 32.0, 59.1, 98.1, 121.8, 124.1,
127.2, 130.5, 134.6, 135.1, 141.2, 145.8, 147.5, 165.1; MF:
2
.974 g), sodium dodecyl sulfate was added as a capping
agent (2 mmol, 0.576 g) while sodium sulfide (10 mmol,
.780 g) was slowly added and the reaction mixture was
+
−
C H N O ; MW: 297; MS (m/z): 298 (M+1) .
1
4
11
5
3
1
0
Compound (Table 3, 5c): IR (KBr, cm ): 3,471,
1
stirred for 5 h. The reaction mixture was filtered and
nanocrystalline zinc sulfide material was dried in an oven
at 120 °C for 2 h. The zinc sulfide nanocrystal was further
calcinized at 400 °C for 2 h. The calcined ZnS nanoparti-
cles were used as catalyst.
3,278, 3,114, 2,191, 1,648, 1,598, 1,508, 1,489; H NMR
(400 MHz, DMSO-d , δ): 1.78 (s, 3H, CH ), 4.87 (s, 1H,
6
3
C-4), 7.41 (d, 2H, Ar–H, J = 8.70 Hz), 7.43 (s, 2H, NH ),
2
1
3
8.25 (d, 2H, Ar–H, J = 8.70 Hz), 12.21 (s, 1H, NH);
C
NMR (100 MHz, DMSO, δ): 9.3, 35.1, 96.1, 120.7, 123.2,
28.1, 135.3, 146.7, 151.3, 154.2, 161.3; MF: C H N O ;
1
1
4
11
5
3
+
Typical experimental procedure for the synthesis
of 4H-pyrano[2,3-c]pyrazoles
MW: 297; MS (m/z): 298 (M+1) .
−
1
Compound (Table 3, 5d): IR (KBr, cm ): 3,409,
1
3
,368, 2,192, 1,515, 1,450; H NMR (400 MHz, DMSO-
To a mixture of hydrazine hydrate (1.0 mmol, 0.050 g) and
ethyl acetoacetate (1.0 mmol, 0.130 g), ZnS nanoparticles
d , δ): 1.62 (s, 3H, CH ), 4.97 (s, 1H, C-4), 6.83 (s, 2H,
6 3
1
3
NH ), 6.96–7.88 (m, 4H, Ar–H), 11.96 (s, 1H, NH);
C
2
(0.5 mmol, 0.050 g) were added and stirred for few min-
NMR (100 MHz, DMSO, δ): 10.3, 27.4, 57.6, 97.6, 121.7,
utes. Then, benzaldehyde (1.0 mmol, 0.106 g) and malon-
onitrile (1.0 mmol, 0.066 g) were added to it and the reac-
tion mixtures were ground by mortar and pestle at room
temperature. The reaction was monitored by thin-layer
chromatographic technique. After completion of the reac-
tion, the crude product was recrystallized from hot ethanol
to afford the pure products. A series of 4H-pyrano[2,3-c]
130.3, 135.3, 137.2, 138.2, 148.7, 156.3, 161.3; M. F:
+
C H BrN O; M. W: 331; MS (m/z): 332 (M+1) .
1
4
11
4
−1
Compound (Table 3, 5e): IR (KBr, cm ): 3,478, 3,247,
1
2,180, 1,596, 1,448; H NMR (400 MHz, DMSO-d , δ):
6
1.74 (s, 3H, CH ), 3.86 (s, 3H, OCH ), 4.64 (s, 1H, C-4),
3
3
6.81 (d, 2H, Ar–H, J = 8.20 Hz), 6.82 (d, 2H, Ar–H,
1
3
J = 8.20 Hz), 7.12 (s, 2H, NH ), 12.13 (s, 1H, NH);
C
2
Scheme 1 synthesis of
R
4
H-pyrano[2,3-c]pyrazoles
CHO
CN
O
O
CN
ZnS nanoparticles
catalyst
grinding, rt
H N NH
2
2
+
N
+
+
OEt
N
H
CN
4
O
NH2
1
2
R
3
5
(a-h)
1
3