Synthesis of spiro[indoline-3,4′-pyrano[2,3-c]pyrazole] and spiro[indoline-3,4′-pyrano[2,3-c]chromene] derivatives using silica-bonded ionic liquids as a recyclable catalyst in aqueous medium

Article abstract of DOI:10.1007/s13738-015-0801-y

Silica-bonded ionic liquids is employed as a recyclable catalyst for the synthesis of spiro[indoline-3,4′-pyrano[2,3-c]pyrazoles] via one-pot condensation reaction of isatin, activated methylene reagents, and 3-methyl-l-phenyl-5-pyrazolone in refluxing aq

Full text of DOI:10.1007/s13738-015-0801-y

J IRAN CHEM SOC
DOI 10.1007/s13738-015-0801-y
ORIGINAL PAPER
Synthesis of spiro[indoline‑3,4′‑pyrano[2,3‑c]pyrazole]
and spiro[indoline‑3,4′‑pyrano[2,3‑c]chromene] derivatives using
silica‑bonded ionic liquids as a recyclable catalyst in aqueous
medium
Khodabakhsh Niknam1 · Abolhassan Piran1 · Zahra Karimi1
Received: 19 August 2015 / Accepted: 11 December 2015
© Iranian Chemical Society 2015
Abstract Silica-bonded ionic liquids is employed as a
recyclable catalyst for the synthesis of spiro[indoline-3,4′-
pyrano[2,3-c]pyrazoles] via one-pot condensation reaction
of isatin, activated methylene reagents, and 3-methyl-l-
phenyl-5-pyrazolone in refluxing aqueous medium in good
to high yields. Also, these silica-bonded ionic liquids were
used as catalysts for the synthesis of spiro[indoline-3,4′-
pyrano[2,3-c]chromene derivatives in refluxing aqueous
medium in high yields. Catalyst could be recycled for sev-
eral times without any additional treatment.
Graphical Abstract Silica-bonded
ionic
liquids
is employed as a recyclable catalyst for the synthe-
sis of spiro[indoline-3,4′-pyrano[2,3-c]pyrazoles] and
spiro[indoline-3,4′-pyrano[2,3-c]chromene via one-pot
condensation reaction of isatin, activated methylene rea-
gents, and 3-methyl-l-phenyl-5-pyrazolone or 4-hydroxy
coumarin respectively in refluxing aqueous medium in
good to high yields.
O
OH
O
O
R
Me
CN
Y
R
CN
Y
+
O
+
O
+
+
O
N
N
H
N
Ph
N
H
O
O
Ph
N
O Si
N
SiO2
NH
Cl
N
O
O
O
O
O
NH2
Me
NH2
H2O/ Reflux
R
R
Y
Y
O
O
N
N
H
H
5a-k
4a-h
Electronic supplementary material The online version of this
article (doi:10.1007/s13738-015-0801-y) contains supplementary
material, which is available to authorized users.
* Khodabakhsh Niknam
niknam@pgu.ac.ir
1
Department of Chemistry, Faculty of Sciences, Persian Gulf
University, Bushehr 75169, Iran
1 3

J IRAN CHEM SOC
Keywords Spiro[indoline-3,4′-pyrano[2,3-c]pyrazoles] ·
Spiro[indoline-3,4′-pyrano[2,3-c]chromenes] · Silica-
bonded ionic liquids · Heterogeneous catalyst · Synthesis ·
Water
readily afford various spirooxindole structures and has
attracted wide attention, and this type of reaction has been
achieved by a number of different catalysts and conditions,
such as SnCl4 [8], triethanolamine [9], basic alumina under
microwave irradiation [10], surfactant TEBA (triethylben-
zylammonium chloride) [11], electrocatalytic multi-com-
ponent assembling [12], β-cyclodextrin [13], NaCl under
sonication [14], ZnS nanoparticles [15], piperidine under
ultrasound irradiation [16], CaCl2 under ultrasonic irradia-
tion [17], 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) [18],
ethylenediammonium diformate (EDDF) [19], SBA-Pr-
NH2 [20], sulfated choline based heteropolyanion [21], and
L-prolin [22].
Immobilization of acidic ionic liquids on solid supports
has been designed and it can offer important advantages in
handling, separation and reuse procedures. Based on eco-
nomic criteria, it is desirable to minimize the amount of
ionic liquid utilized in a potential process. Immobilized
acidic ionic liquids have been used as novel solid catalysts,
e.g., for esterification, nitration reactions [23], acetal for-
mation [24], Baeyer–Villiger reaction [25], synthesis of
α-aminonitriles [26] bis-pyrazolones [27], chromenes [28],
4,4-(arylmethylene)-bis-(3-methyl-1-phenyl-1H-pyrazol-
5-ols) [29], 12-aryl-8,9,10,12-tetrahydrobenzo[a]-xanthen-
11-ones [30], and 1-(benzothiazolylamino)-phenylmethyl-
2-naphthols [31].
Introduction
Spirooxindoles are commonly occurring heterocyclic ring
systems and are important structural motifs found in many
natural products and pharmaceuticals [1, 2]. The key struc-
tural characteristic of these compounds is the spiro ring
fused at the C3 position of the oxindole core with varied
heterocyclic motifs [3]. Among them, those with an indole
moiety exhibit antibacterial and antifungal activities [4,
5]. The significant biological activity and recent synthetic
advances of these natural products encouraged the develop-
ment of biologically promising analogs that would be more
efficacious and selective than the original natural prod-
ucts [6]. The privileged spirooxindole skeletons have high
potential for the development of some medicinal agents [7].
Two representative examples are NITD609 (1) and MI-888
(2) in Fig. 1.
The one-pot condensation reaction of isatin, activated
methylene reagents, and 1,3-dicarbonyl compounds could
In this regard, we introduced a series of silica-bonded
ionic liquids such as: silica propyl imidazolium chloride
([Sipim]Cl), silica propyl imidazolium triflate ([Sipim]
OTf), N-(3-silicapropyl) imidazolium hydrogen sulfate
([Sipim]HSO4), and N-(3-silicapropyl) imidazolium hydro-
gen phosphate ([Sipim]H2PO4) as recyclable catalysts and
investigated their catalytic activities in organic transforma-
tions [26–28] (Scheme 1).
In continuation of our study on the preparation of solid
acids and bases and investigation of their applications in
heterocyclic synthesis [32–40], Herein, we describe the
synthesis of spirooxindole derivatives via three-component
F
Cl
F
H
N
Cl
Cl
O
NH
N
H
O
H
N
N
H
NH
Cl
OH
O
NITD609 (1)
MI-888 (2)
Fig. 1 Two representative examples of spirooxindoles NITD609 and
MI-888
Scheme 1 The structure of
silica-bonded ionic liquids
O
O
O Si
N
SiO2
O
O
Si
N
SiO2
NH
NH
HSO4
H2PO4
O
[Sipim]HSO4
[Sipim]H2PO4
O
O
O
Si
N
SiO2
O
O
Si
N
SiO2
NH
NH
Cl
O
OTf
[Sipim]Cl
[Sipim]OTf
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J IRAN CHEM SOC
Scheme 2 Synthesis of
spirooxindole derivatives
Ph
N
Me
O
N
N
O
N
Ph
NH2
Me
R
Y
3a
O
N
H
4a-h
O
[Sipim]Cl
CN
Y
R
+
O
H2O/ Reflux
N
H
OH
O
O
NH2
O
R = H, Cl, NO2
Y = CN, COOMe, COOEt
R
O
O
Y
O
N
H
3b
5a-k
condensation reaction of isatin, reactive methylene rea-
gents, and 1,3-dicarbonyl compounds using silica-bonded
N-propylimidazolium chloride ([Sipim]Cl) in aqueous
media at reflux conditions (Scheme 2).
General procedure for the synthesis of spirooxindole
derivatives
A mixture of isatin (1 mmol), reactive methylene com-
pound (1 mmol) and 1,3-dicarbonyl compound (1 mmol)
in the presence of [Sipim]Cl (0.05 g) in water (5 mL)
was refluxed with stirring in an oil bath. The progress of
the reaction was monitored by TLC. After completion of
the reaction, the mixture was filtered and remaining was
washed with warm ethanol (3 × 10 mL) in order to sepa-
rate [Sipim]Cl catalyst. After cooling the ethanol phase, the
precipitates were filtered. The crude products were purified
by recrystallization from ethanol (95 %).
Experimental
Chemicals and reagents
Chemicals were purchased from Merck and Aldrich Chemi-
cal Companies and use as is. 1H-NMR spectra we recorded
on a Bruker Avance (500 MHz DRX) or Bruker Ultrash-
ield (400 MHz) using DMSO-d6 as deuterated solvent and
with tetramethylsilane (TMS) as internal standard. Melting
points were determined in open capillary tubes in a Barn-
stead Electrothermal 9100 BZ circulating oil melting point
apparatus and uncorrected. Reactions were monitored by
TLC using silica gel Poly Gram SILG/UV254 plates. All the
products were characterized by IR, NMR, Mass spectra and
known compounds compared with those reported in litera-
ture [11–20]. Solid silica-supported bases such as [Sipim]
HSO4, [Sipim]H2PO4, [Sipim]OTf, and [Sipim]Cl were pre-
pared according to our reported procedures [26–28].
6′‑Amino‑3′‑methyl‑2‑oxo‑1′‑phenyl‑1′H‑spiro[indoline‑
3,4′‑pyrano[2,3‑c]pyrazole]‑5′‑carboxylate (4a) (Table 2,
entry 1)
mp 235–237 °C, (Ref.: [12] 236–237 °C); 1H-NMR
(400 MHz, DMSO-d6): δ (ppm) 1.55 (s, 3H, CH3), 6.91–
7.09 (m, 2H, Ar), 7.18 (d, 1H, J = 6.8 Hz, Ar), 7.25–7.42
(m, 2H, Ar), 7.48–7.56 (m, 2H, Ar), 7.59 (s, 2H, NH2),
7.79 (d, 2H, J = 7.3 Hz, Ar), 10.75 (s, 1H, NH). 13C-NMR
(125 MHz, DMSO-d6): δ 12.2, 48.2, 56.6, 96.8, 110.3,
118.4, 120.6, 123.1, 125.4, 127.0, 129.8, 129.9, 132.6,
137.7, 142.0, 144.4, 145.4, 161.5, 178.0.
Preparation of silica propyl imidazolium chloride
[Sipim]Cl
6′‑Amino‑5‑chloro‑3′‑methyl‑2‑oxo‑1′‑phenyl‑1′H‑spiro[
indoline‑3,4′‑pyrano[2,3‑c]pyrazole]‑5′‑carboxylate (4b)
(Table 2, entry 2)
Silicapropyl chloride (10.0 g) was added to a flask con-
taining 100 mL of anhydrous toluene and a large excess of
imidazole (10.0 g). The reaction mixture was refluxed with
stirring for 24 h. Then, the reaction mixture was cooled to
room temperature, transferred to a vacuum glass filter, and
washed with toluene, ethanol, and methanol in turn. The
silica chemically bonded with imidazolium ([Sipim]Cl)
was dried under vacuum at 50 °C for 4 h [26].
mp 232–233 °C, (Ref.: [14] 232–234 °C); 1H-NMR
(400 MHz, DMSO-d6): δ (ppm) 1.60 (s, 3H, CH3), 6.97 (d,
1H, J = 8.3 Hz, Ar), 7.32–7.39 (m, 3H, Ar), 7.53 (t, 2H,
J = 8.0 Hz, Ar), 7.65 (s, 2H, NH2), 7.79 (d, 2H, J = 7.8 Hz,
Ar), 10.90 (s, 1H, NH). 13C-NMR (100 MHz, DMSO-d6):
1 3

J IRAN CHEM SOC
δ 12.2, 48.5, 56.0, 96.1, 111.8, 118.4, 120.7, 125.7, 127.1,
127.2, 129.7, 129.9, 134.8, 137.7, 140.9, 144.2, 145.5,
161.5, 177.8.
Ethyl‑6′‑amino‑3′‑methyl‑2‑oxo‑1′‑phenyl‑1′H‑spiro[in
doline‑3,4′‑pyrano[2,3‑c]pyrazole]‑5′‑carboxylate (4f)
(Table 2, entry 6)
6′‑Amino‑5‑nitro‑3′‑methyl‑2‑oxo‑1′‑phenyl‑1′H‑spiro[i
ndoline‑3,4′‑pyrano[2,3‑c]pyrazole]‑5′‑carboxylate (4c)
(Table 2, entry 3)
mp 239–241 °C, (Ref.: [14] 238–240 °C); 1H-NMR
(400 MHz, DMSO-d6): δ (ppm) 0.75 (t, 3H, J = 7.2 Hz
CH3), 1.59 (s, 3H, CH3), 3.68–3.81 (m, 2H, OCH2),
6.84–6.92 (m, 2H, Ar), 6.97 (d, 1H, J = 7.1 Hz, Ar),
7.17 (dt, 1H, J1 = 7.1, J2 = 1.2 Hz, Ar), 7.34 (t, 1H,
J = 7.3 Hz, Ar), 7.52 (t, 2H, J = 8.1 Hz, Ar), 7.81 (d, 2H,
J = 7.6 Hz, Ar), 8.21 (s, 2H, NH2), 10.52 (s, 1H, NH).
13C-NMR (125 MHz, DMSO-d6): δ 12.2, 13.6, 47.9,
59.5, 75.0, 98.7, 109.3, 120.4, 122.2, 123.7, 126.8, 128.2,
129.9, 136.2, 137.8, 142.7, 144.4, 144.7, 161.8, 168.3,
179.7.
mp 227–229 °C, (Ref.: [14] 226–228 °C); 1H-NMR
(400 MHz, DMSO-d6): δ (ppm) 1.60 (s, 3H, CH3), 7.18
(d, 1H, J = 8.6 Hz, Ar), 7.37 (t, 1H, J = 7.3 Hz, Ar), 7.53
(t, 2H, J = 7.9 Hz, Ar), 7.74 (s, 2H, NH2), 7.80 (d, 2H,
J = 7.8 Hz, Ar), 8.23 (d, 1H, J = 1.8 Hz, Ar), 8.27 (dd, 1H,
J1 = 8.7, J2 = 2.1 Hz, Ar), 11.49 (s, 1H, NH). 13C-NMR
(100 MHz, DMSO-d6): δ 11.8, 47.9, 56.0, 94.9, 110.2,
117.8, 120.4, 121.0, 126.5, 126.7, 129.4, 133.3, 137.1,
143.1, 143.6, 145.2, 147.7, 161.2, 178.1.
Ethyl‑6′‑amino‑5‑chloro‑3′‑methyl‑2‑oxo‑1′‑phenyl‑1′H‑s
piro[indoline‑3,4′‑pyrano[2,3‑c]pyrazole]‑5′‑carboxylate
(4 g) (Table 2, entry 7)
Methyl‑6′‑amino‑5‑chloro‑3′‑methyl‑2‑oxo‑1′‑phenyl‑1′H‑
spiro[indoline‑3,4′‑pyrano[2,3‑c]pyrazole]‑5′‑carboxylate
(4d) (Table 2, entry 4)
mp 246–247 °C, (Ref.: [15] 246–248 °C); 1H-NMR
(400 MHz, DMSO-d6): δ (ppm) 0.79 (t, 3H, J = 7.1 Hz
CH3), 1.63 (s, 3H, CH3), 3.72–3.85 (m, 2H, OCH2), 6.87
(d, 1H, J = 8.3 Hz, Ar), 7.12 (d, 1H, J = 2.0 Hz, Ar),
7.23 (dd, 1H, J1 = 8.3, J2 = 2.3 Hz, Ar), 7.35 (t, 1H,
J = 7.4 Hz, Ar), 7.52 (t, 2H, J = 7.9 Hz, Ar), 7.82 (d,
2H, J = 7.8 Hz, Ar), 8.27 (s, 2H, NH2), 10.66 (s, 1H,
NH). 13C-NMR (100 MHz, DMSO-d6): δ 12.2, 13.6, 48.2,
59.6, 74.5, 98.0, 110.7, 120.6, 124.0, 126.2, 126.9, 128.1,
129.9, 137.8, 138.4, 141.6, 144.5, 144.6, 161.9, 168.2,
179.5.
mp 224–226 °C; 1H-NMR (500 MHz, DMSO-d6): δ
(ppm) 1.61 (s, 3H, CH3), 3.34 (s, 3H, OCH3), 6.88
(d, 1H, J = 10.0 Hz, Ar), 7.11 (d, 1H, J = 2.5 Hz, Ar),
7.22 (dd, 1H, J1 = 10.0, J2 = 2.5 Hz, Ar), 7.53 (t, 1H,
J = 10.0 Hz, Ar), 7.52 (t, 2H, J = 10.0 Hz, Ar), 7.82 (d,
2H, J = 10.0 Hz, Ar), 8.21 (s, 2H, NH2), 10.66 (s, 1H,
NH). 13C-NMR (125 MHz, DMSO-d6): δ 12.2, 48.3, 51.0,
74.8, 98.0, 110.7, 120.6, 124.0, 126.2, 126.9, 128.2, 129.9,
137.8, 138.2, 141.3, 144.4, 144.6, 161.8, 168.3, 179.4. Anal
calcd for C22H17ClN4O4: C, 60.49; H, 3.92; Cl, 8.12; N,
12.83. Found: C, 60.18; H, 3.98; N, 12.71.
Ethyl‑6′‑amino‑5‑nitro‑3′‑methyl‑2‑oxo‑1′‑phenyl‑1′H‑sp
iro[indoline‑3,4′‑pyrano[2,3‑c]pyrazole]‑5′‑carboxylate
(4 h) (Table 2, entry 8)
Methyl‑6′‑amino‑5‑nitro‑3′‑methyl‑2‑oxo‑1′‑phenyl‑1′H‑s
piro‑[indoline‑3,4′‑pyrano[2,3‑c]pyrazole]‑5′‑carboxylate
(4e) (Table 2, entry 5)
mp 267–269 °C, (Ref.: [15] 268–270 °C); 1H-NMR
(400 MHz, DMSO-d6): δ (ppm) 0.78 (t, 3H, J = 7.0 Hz
CH3), 1.62 (s, 3H, CH3), 3.71–3.83 (m, 2H, OCH2), 7.09
(d, 1H, J = 8.8 Hz, Ar), 7.36 (t, 1H, J = 7.4 Hz, Ar),
7.53 (t, 2H, J = 8.0 Hz, Ar), 7.83 (d, 2H, J = 7.5 Hz,
Ar), 7.98 (d, 1H, J = 2.3 Hz, Ar), 8.2 (dd, 1H, J1 = 8.9,
J2 = 2.3 Hz, Ar), 8.34 (s, 2H, NH2), 11.28 (s, 1H, NH).
13C-NMR (100 MHz, DMSO-d6): δ 12.3, 13.7, 48.0,
59.7, 74.0, 97.3, 109.6, 120.7, 125.9, 127.0, 129.4, 129.9,
137.4, 137.7, 143.0, 144.3, 144.8, 149.1, 162.1, 167.9,
180.3.
1
mp 241–243 °C. H-NMR (500 MHz, DMSO-d6): δ 1.61
(s, 3H, CH3), 3.33 (s, 3H, OCH3), 7.09 (d, 1H, J = 8.8 Hz,
Ar), 7.36 (t, 1H, J = 7.3 Hz, Ar), 7.53 (t, 2H, J = 7.8 Hz,
Ar), 7.83 (d, 2H, J = 7.8 Hz, Ar), 7.97 (d, 1H, J = 2.0 Hz,
Ar), 8.18 (dd, 1H, J1 = 8.5, J2 = 2.2 Hz, Ar), 8.27 (s, 2H,
NH2), 11.27 (s, 1H, NH).13C-NMR (125 MHz, DMSO-d6):
δ 12.3, 48.2, 51.1, 74.3, 97.3, 109.6, 120.7, 125.9, 127.0,
129.4, 129.8, 137.2, 137.8, 143.0, 144.2, 144.8, 148.9,
161.9, 168.1, 180.2. Anal calcd for C22H17N5O6: C, 59.06;
H, 3.83; N, 15.65. Found: C, 58.78; H, 3.90; N, 15.51.
1 3

J IRAN CHEM SOC
6′‑Amino‑1,3′‑dimethyl‑2‑oxo‑1′‑phenyl‑1′H‑spiro[indolin
e‑3,4′‑pyrano[2,3‑c]pyrazole]‑5′‑carboxylate (4i) (Table 2,
entry 9)
125.5, 126.5, 129.3, 134.2, 135.5, 141.6, 152.6, 155.9,
158.9, 159.0, 177.5.
2′‑Amino‑5‑nitro‑2,5′‑dioxo‑5′H‑spiro[indoline‑3,4′‑pyran
o[2,3‑c]chromene]‑3′‑carbonitrile (5c) (Table 3, entry 3)
mp 224–226 °C, (Ref.: [12] 226–227 °C); 1H-NMR
(400 MHz, DMSO-d6): δ (ppm) 1.46 (s, 3H, CH3),
3.25 (s, 3H, CH3), 7.10–7.18 (m, 2H, Ar), 7.25 (d,
1H, J = 8.3 Hz, Ar), 7.34–7.42 (m, 2H, Ar), 7.52 (t,
2H, J = 7.9 Hz, Ar), 7.63 (s, 2H, NH2), 7.79 (dd, 2H,
J1 = 8.7, J2 = 1.0 Hz, Ar). 13C-NMR (125 MHz, DMSO-
d6): δ 12.2, 27.0, 47.9, 56.1, 96.6, 109.4, 118.3, 120.6,
123.8, 125.0, 127.1, 129.9, 131.8, 137.7, 143.5, 144.3,
145.4, 161.6, 176.3.
1
mp > 270 °C; H-NMR (400 MHz, DMSO-d6): δ 7.09 (d,
1H, J = 8.8 Hz, Ar), 7.52 (d, 1H, J = 7.8 Hz, Ar), 7.57
(dt, 1H, J1 = 7.7, J2 = 1.0 Hz, Ar), 7.79 (dt, 1H, J1 = 7.4,
J2 = 1.5 Hz, Ar), 7.86 (s, 2H, NH2), 7.96 (dd, 1H, J1 = 8.0,
J2 = 1.5 Hz, Ar), 8.22 (dd, 1H, J1 = 8.5, J2 = 2.5 Hz, Ar),
8.37 (d, 1H, J = 2.5 Hz, Ar), 11.43 (s, 1H, NH). 13C-NMR
(100 MHz, DMSO-d6): δ 48.2, 56.1, 100.7, 110.2, 113.2,
117.2, 117.3, 121.1, 123.3, 125.5, 126.8, 134.3, 134.5,
143.2, 149.1, 152.6, 156.3, 159.2, 159.3, 178.4. Anal calcd
for C20H10N4O6: C, 59.71; H, 2.51; N, 13.93. Found: C,
59.42; H, 2.57; N, 13.80.
6′‑Amino‑3′,5‑dimethyl‑2‑oxo‑1′‑phenyl‑1′H‑spiro[indolin
e‑3,4′‑pyrano[2,3‑c]pyrazole]‑5′‑carboxylate (4j) (Table 2,
entry 10)
mp > 270 °C, (Ref.: [12] 288–289 °C); 1H-NMR
(400 MHz, DMSO-d6): δ (ppm) 1.51 (s, 3H, CH3), 2.19
(s, 3H, CH3), 6.78 (d, 1H, J = 6.4 Hz, Ar), 6.95 (s, 1H,
Ar), 7.01–7.04 (m, 1H, Ar), 7.29–7.32 (m, 1H, Ar), 7.45–
7.49 (m, 4H, Ar and NH2), 7.74 (d, 2H, J = 6.4 Hz, Ar),
10.57 (s, 1H, NH). 13C-NMR (100 MHz, DMSO-d6): δ
19.4, 21.4, 48.7, 97.4, 110.4, 118.9, 121.0, 126.2, 127.4,
130.3, 130.4, 132.5, 133.2, 138.1, 140.0, 144.9, 145.8,
161.8, 178.3.
Methyl‑2′‑amino‑2,5′‑dioxo‑5′H‑spiro[indoline‑3,4′‑pyran
o[2,3‑c]chromene]‑3′‑ carboxylate (5d) (Table 3, entry 4)
mp > 270 °C, (Ref. [11] 275–277 °C); 1H-NMR (400 MHz,
DMSO-d6): δ 3.33 (s, 3H, OCH3), 6.74–6.85 (m, 2H, Ar),
7.02 (d, 1H, J = 7.3 Hz, Ar), 7.11 (t, 1H, J = 7.5 Hz, Ar),
7.44 (d, 1H, J = 8.0 Hz, Ar), 7.51 (t, 1H, J = 7.5 Hz, Ar),
7.73 (t, 1H, J = 7.4 Hz, Ar), 8.04 (d, 1H, J = 7.8 Hz, Ar),
8.09 (s, 2H, NH2), 10.45 (s, 1H, NH). 13C-NMR (100 MHz,
DMSO-d6): δ 47.9, 50.9, 76.3, 104.3, 108.9, 112.9, 116.8,
121.5, 123.3, 123.7, 125.3, 128.5, 133.9, 134.9, 144.4,
152.3, 154.3, 158.2, 158.9, 167.6, 179.4.
2′‑Amino‑2,5′‑dioxo‑5′H‑spiro[indoline‑3,4′‑pyrano[2,
3‑c]chromene]‑3′‑carbonitrile (5a) (Table 3, entry 1)
mp > 270 °C, (Ref. [18] 292–294 °C); 1H-NMR (400 MHz,
DMSO-d6): δ 6.86 (d, 1H, J = 8.0 Hz, Ar), 6.94 (t, 1H,
J = 7.0 Hz, Ar), 7.20–7.25 (m, 2H, Ar), 7.50 (d, 1H,
J = 8.3 Hz, Ar), 7.55 (t, 1H, J = 7.7 Hz, Ar), 7.68 (s, 2H,
NH2), 7.77 (t, 1H, J = 7.9 Hz, Ar), 7.95 (dd, 1H, J1 = 8.0,
J2 = 1.5 Hz, Ar), 10.69 (s, 1H, NH). 13C-NMR (100 MHz,
DMSO-d6): δ 48.1, 57.5, 101.9, 110.0, 112.9, 117.2, 117.5,
122.5, 123.1, 124.6, 125.5, 129.4, 133.5, 134.2, 142.7,
152.5, 155.6, 158.8, 158.9, 177.6.
Methyl‑2′‑amino‑5‑chloro‑2,5′‑dioxo‑5′H‑spiro[indoline‑
3,4′‑pyrano[2,3‑c]chromene]‑3′‑carboxylate (5e) (Table 3,
entry 5)
mp > 270 °C, (Ref. [20] 279–281 °C); 1H-NMR (400 MHz,
DMSO-d6): δ 3.35 (s, 3H, OCH3), 6.76 (d, 1H, J = 8.3 Hz,
Ar), 7.16 (dd, 1H, J1 = 8.1, J2 = 2.2 Hz, Ar), 7.20 (d, 1H,
J = 2.2 Hz, Ar), 7.46 (d, 1H, J = 8.3 Hz, Ar), 7.53 (t, 1H,
J = 7.7 Hz, Ar), 7.75 (dt, 1H, J1 = 7.8, J2 = 1.5 Hz, Ar),
8.04 (dd, 1H, J1 = 7.9, J2 = 1.5 Hz, Ar), 8.13 (s, 2H, NH2),
10.58 (s, 1H, NH). 13C-NMR (100 MHz, DMSO-d6): δ
48.2, 50.9, 75.8, 103.5, 110.1, 113.1, 116.8, 123.5, 124.1,
125.3, 125.4, 128.2, 133.9, 137.0, 143.4, 152.4, 154.7,
158.4, 158.4, 159.0, 167.5, 179.2.
2′‑Amino‑5‑chloro‑2,5′‑dioxo‑5′H‑spiro[indoline‑3,4′‑py
rano[2,3‑c]chromene]‑3′‑carbonitrile (5b) (Table 3, entry
2)
1
mp > 270 °C, (Ref. [20] >300 °C); H-NMR (400 MHz,
DMSO-d6): δ 6.87 (d, 1H, J = 8.3 Hz, Ar), 7.27 (dd,
1H, J1 = 8.3, J2 = 2.2 Hz, Ar), 7.45 (d, 1H, J = 2.3 Hz,
Ar), 7.51 (d, 1H, J = 8.3 Hz, Ar), 7.56 (dt, 1H, J1 = 7.7,
J2 = 0.8 Hz, Ar), 7.75 (s, 2H, NH2), 7.79 (dt, 1H, J1 = 7.8,
J2 = 1.5 Hz, Ar), 7.95 (dd, 1H, J1 = 7.9, J2 = 1.3 Hz, Ar),
10.82 (s, 1H, NH). 13C-NMR (100 MHz, DMSO-d6): δ
48.3, 56.8, 101.2, 111.3, 113.1, 117.2, 117.4, 123.2, 125.1,
Methyl‑2′‑amino‑5‑bromo‑2,5′‑dioxo‑5′H‑spiro[indoline‑
3,4′‑pyrano[2,3‑c]chromene]‑3′‑carboxylate (5f) (Table 3,
entry 6)
mp > 270 °C, (Ref. [20] 288–290 °C); 1H-NMR (400 MHz,
DMSO-d6): δ 3.35 (s, 3H, OCH3), 6.72 (d, 1H, J = 8.0 Hz,
Ar), 7.26–7.33 (m, 2H, Ar), 7.46 (d, 1H, J = 8.3 Hz, Ar),
1 3

J IRAN CHEM SOC
7.53 (t, 1H, J = 7.6 Hz, Ar), 7.75 (t, 1H, J = 7.9 Hz, Ar),
8.04 (dd, 1H, J1 = 8.0, J2 = 1.2 Hz, Ar), 8.13 (s, 2H, NH2),
10.59 (s, 1H, NH). 13C-NMR (100 MHz, DMSO-d6): δ
48.1, 51.0, 75.8, 103.5, 110.7, 113.1, 116.8, 123.5, 125.3,
126.7, 131.1, 133.9, 137.4, 143.8, 152.4, 154.7, 158.4,
159.0, 167.5, 179.1.
Ethyl‑2′‑amino‑5‑bromo‑2,5′‑dioxo‑5′H‑spiro[indoline‑3,
4′‑pyrano[2,3‑c]chromene]‑3′‑carboxylate (5j) (Table 3,
entry 10)
mp > 270 °C, (Ref. [20] 280–282 °C); 1H-NMR (400 MHz,
DMSO-d6): δ 0.87 (t, 3H, J = 7.2 Hz, CH3), 3.74–3.86
(m, 2H, OCH2), 6.71 (d, 1H, J = 8.0 Hz, Ar), 7.27–7.33
(m, 2H, Ar), 7.46 (d, 1H, J = 8.5 Hz, Ar), 7.53 (t, 1H,
J = 7.5 Hz, Ar), 7.75 (dt, 1H, J1 = 7.8, J2 = 1.3 Hz, Ar),
8.03 (d, 1H, J = 8.0 Hz, Ar), 8.20 (s, 2H, NH2), 10.59 (s,
1H, NH). 13C-NMR (100 MHz, DMSO-d6): δ 13.7, 48.0,
59.7, 75.5, 103.6, 110.7, 113.1, 116.8, 123.4, 125.3, 126.8,
131.0, 133.9, 137.6, 144.0, 152.4, 154.6, 158.4, 159.1,
167.5, 179.1.
Methyl‑2′‑amino‑5‑nitro‑2,5′‑dioxo‑5′H‑spiro[indoline‑3,
4′‑pyrano[2,3‑c]chromene]‑3′‑carboxylate (5 g) (Table 3,
entry 7)
1
mp > 270 °C; H-NMR (400 MHz, DMSO-d6): δ 3.36 (s,
3H, OCH3), 6.95 (d, 1H, J = 8.5 Hz, Ar), 7.46 (d, 1H,
J = 8.3 Hz, Ar), 7.54 (t, 1H, J = 7.7 Hz, Ar), 7.76 (t,
1H, J = 7.9 Hz, Ar), 8.06 (dd, 1H, J1 = 8.0, J2 = 1.5 Hz,
Ar), 8.09 (d, 1H, J = 2.2 Hz, Ar), 8.13 (dd, 1H, J1 = 8.5,
J2 = 2.2 Hz, Ar), 8.20 (s, 2H, NH2), 11.21 (s, 1H, NH).
13C-NMR (100 MHz, DMSO-d6): δ 48.0, 51.0, 75.3, 102.9,
108.8, 113.1, 116.9, 119.8, 123.5, 125.3, 126.1, 134.1,
136.0, 142.4, 151.1, 152.4, 155.1, 158.7, 159.1, 167.3,
180.2. Anal calcd for C21H13N3O8: C, 57.94; H, 3.01; N,
9.65. Found: C, 57.65; H, 3.07; N, 9.38.
Ethyl‑2′‑amino‑5‑nitro‑2,5′‑dioxo‑5′H‑spiro[indoline‑3,
4′‑pyrano[2,3‑c]chromene]‑3′‑carboxylate (5k) (Table 3,
entry 11)
mp 267–268 °C; 1H-NMR (400 MHz, DMSO-d6): δ 0.85 (t,
3H, J = 7.1 Hz, CH3), 3.80 (q, 2H, J = 7.1 Hz, OCH2), 6.96
(d, 1H, J = 8.5 Hz, Ar), 7.46 (d, 1H, J = 8.3 Hz, Ar), 7.55
(t, 1H, J = 7.6 Hz, Ar), 7.76 (dt, 1H, J1 = 7.8, J2 = 1.0 Hz,
Ar), 8.05 (dd, 1H, J1 = 7.9, J2 = 1.7 Hz, Ar), 8.11 (d, 1H,
J = 2.5 Hz, Ar), 8.15 (dd, 1H, J1 = 8.5, J2 = 2.3 Hz, Ar),
8.28 (s, 2H, NH2), 11.21 (s, 1H, NH). 13C-NMR (100 MHz,
DMSO-d6): δ 13.7, 47.9, 59.8, 74.9, 103.0, 108.9, 113.1,
116.9, 119.9, 123.5, 125.3, 126.1, 134.1, 136.2, 142.4,
151.3, 152.4, 155.1, 158.7, 159.3, 167.2, 180.2. Anal calcd
for C22H15N3O8: C, 58.80; H, 3.36; N, 9.35. Found: C,
58.49; H, 3.39; N, 9.11.
Ethyl‑2′‑amino‑2,5′‑dioxo‑5′H‑spiro[indoline‑3,4′‑pyrano
[2,3‑c]chromene]‑3′‑carboxylate (5 h) (Table 3, entry 8)
mp 253–255 °C, (Ref. [18] 252–254 °C); 1H-NMR
(400 MHz, DMSO-d6): δ 0.83 (t, 3H, J = 7.2 Hz, CH3),
3.71–3.83 (m, 2H, OCH2), 6.75 (d, 1H, J = 7.8 Hz,
Ar), 6.81 (dt, 1H, J1 = 7.5, J2 = 0.8 Hz, Ar), 7.02 (d,
1H, J = 6.8 Hz, Ar), 7.13 dt, 1H, J1 = 7.7, J2 = 1.2 Hz,
Ar), 7.45 (d, 1H, J = 8.3 Hz, Ar), 7.53 (dt, 1H, J1 = 7.7,
J2 = 1.0 Hz, Ar), 7.75 (dt, 1H, J1 = 7.9, J2 = 1.5 Hz, Ar),
8.04 (dd, 1H, J1 = 8.0, J2 = 1.2 Hz, Ar), 8.15 (s, 2H, NH2),
10.43 (s, 1H, NH). 13C-NMR (100 MHz, DMSO-d6): δ
13.6, 47.8, 59.6, 76.0, 104.3, 108.9, 112.9, 116.8, 121.5,
123.3, 123.7, 125.3, 128.4, 133.9, 135.1, 144.6, 152.3,
154.2, 158.2, 159.0, 167.6, 179.3.
Results and discussion
The catalytic activity of silica-bonded ionic liquids such
as [Sipim]HSO4, [Sipim]H2PO4, [Sipim]OTf, and [Sipim]
Cl was investigated as a heterogeneous catalysts in one-pot
synthesis of spiro[indoline-3,4′-pyrano[2,3-c]pyrazoles]
through three-component reaction of isatin, malononitrile,
and 3-methyl-l-phenyl-5-pyrazolone and the results are
summarized in Table 1.
Ethyl‑2′‑amino‑5‑chloro‑2,5′‑dioxo‑5′H‑spiro[indoline‑3,
4′‑pyrano[2,3‑c]chromene]‑3′‑carboxylate (5i) (Table 3,
entry 9)
For this purpose, the reaction between isatin (1 mmol),
malononitrile (1 mmol), and 3-methyl-l-phenyl-5-pyra-
zolone (1 mmol) was selected as a model reaction in
aqueous media in order to establish the feasibility of the
strategy and optimize the reaction conditions. All of these
silica immobilized propyl imidazolium salts were accom-
plished this three-component condensation reaction in
aqueous media at refluxing conditions. The model reaction
was converted into corresponding product (4a) in a higher
yield using solid [Sipim]Cl (0.05 g) as catalyst (Table 1,
entry 5). The lower amounts of [Sipim]Cl (0.03 g) was
mp > 270 °C, (Ref. [20] 275–277 °C); 1H-NMR (400 MHz,
DMSO-d6): δ 0.86 (t, 3H, J = 7.2 Hz, CH3), 3.74–3.86
(m, 2H, OCH2), 6.75 (d, 1H, J = 8.0 Hz, Ar), 7.15–7.22
(m, 2H, Ar), 7.46 (d, 1H, J = 8.3 Hz, Ar), 7.53 (t, 1H,
J = 7.7 Hz, Ar), 7.75 (dt, 1H, J1 = 7.8, J2 = 1.3 Hz, Ar),
8.03 (dd, 1H, J1 = 7.8, J2 = 1.3 Hz, Ar), 8.20 (s, 2H, NH2),
10.58 (s, 1H, NH). 13C-NMR (100 MHz, DMSO-d6): δ
13.7, 48.1, 59.7, 75.5, 103.6, 110.1, 113.1, 116.8, 123.4,
124.1, 125.3, 125.4, 128.1, 133.9, 137.2, 143.6, 152.4,
154.6, 158.4, 159.1, 167.5, 179.2.
1 3

J IRAN CHEM SOC
Table 1 Condensation reaction
of isatin, malononitrile with
3-methyl-l-phenyl-5-pyrazolone
in the presence of different
amounts of catalysts
Ph
N
N
O
O
Me
NH2
CN
Me
Catalyst
CN
CN
O
+
+
O
N
N
Ph
O
H2O (Reflux)
N
H
N
H
4a
Entry
Catalyst
Catalyst loading
Time
(min)
15
Yieldb %
(g)
O
1
0.05
90
N
N
N
O Si
SiO2
NH
HSO4
O
O
2
3
0.05
0.05
0.03
0.05
0.07
0.05
0.05
15
15
20
15
15
60
50
90
85
85
95
95
71
79
O Si
SiO2
NH
H2PO4
O
O
O Si
SiO2
SiO2
SiO2
SiO2
SiO2
SiO2
SiO2
NH
OTf
O
O
O Si
4
N
NH
Cl
O
O
O Si
5
N
N
N
N
N
NH
Cl
O
O
6
O Si
NH
Cl
O
7c
8d
9e
O
O Si
NH
Cl
O
O
O Si
NH
Cl
O
O
O Si
0.05
90
70
NH
Cl
O
HN
10
11
12
13
14
NH
Cl
Reaction conditions: isatin
(1 mmol), malononitrile
(1 mmol), and 3-methyl-l-
phenyl-5-pyrazolone (1 mmol)
in refluxing water (5 mL)
0.20
0.20
0.20
0.20
-
15
15
80
75
HN
NH
HSO4
HN
NH
H2PO4
15
75
a
Isolated yield. b The reaction
was performed at 45 °C.
c The reaction was performed
at 80 °C. d The reaction was
performed at 120 °C under
solvent-free conditions
HN
NH
Br
15
80
Without catalyst
120
trace
converted the model reaction in longer reaction time and
lower yield (Table 1, entry 4) and using higher amounts
of the catalyst (0.07 g) did not improve the result to an
appreciable extent (Table 1, entry 6). The model reac-
tion was examined at 120 °C and solvent-free conditions
(Table 1, entry 9) and lower temperature 45 and 80 °C in
water at solvent (Table 1, entries 7 and 8) gave the cor-
responding product in longer reaction time and lower
yields. The model reaction was treated with available
ionic liquids such as imidazolium chloride, imidazolium
bromide, imidazolium hydrogen sulfate, and imidazolium
hydrogen phosphate and the corresponding product (4a)
was obtained in the presence of 0.20 mmol of these ionic
liquids after 15 min in 75–80 % yields (Table 1, entries
10–13). The optimum conditions was isatin (1 mmol),
methylene active compound (1 mmol), 3-methyl-l-phenyl-
5-pyrazolone (1 mmol), and [Sipim]Cl (0.05 g) in reflux-
ing aqueous media.
1 3

J IRAN CHEM SOC
Table 2 Preparation of spiro[indoline-3,4′-pyrano[2,3-c]pyrazole] derivatives catalyzed by [Sipim]Cl in water at reflux conditions
Entry
R
Y
Product
Time
(min)
Yield mp oC
Lit.
mp
(%)b
(oC)
Ph
N
235-
237
236-
237
N
O
NH2
CN
Me
[12]
H
CN
15
20
15
75
60
95
1
O
N
H
4a
Ph
N
232-
233
232-
234
[14]
N
O
NH2
CN
Me
Cl
NO2
Cl
CN
CN
85
2
3
4
5
Cl
O
N
H
4b
Ph
N
227-
229
226-
228
[14]
N
O
NH2
CN
Me
90
O2N
O
N
H
4c
Ph
N
224-
226
-
-
N
O
NH2
COOMe
Me
COOMe
75
Cl
O
N
H
4d
Ph
N
241-
243
N
O
NH2
Me
NO2 COOMe
80
O2N
COOMe
O
N
H
4e
The reaction can tolerate isatin and some of its deriva-
tives carrying both electron-withdrawing group such as
NO2 and halogen such as Cl and the results were reason-
able (Table 2). Beside malonitrile, other methylene active
compound such as methyl acetoacetate and ethyl acetoac-
etate reacted under optimized conditions and gave the cor-
responding products in high yields (Table 2, entries 4–8).
In addition, 4-hydroxy coumarin as 1,3-dicarbonyl com-
pound (enol form) was treated with isatin and methylene
active compounds under optimized conditions and the
corresponding spiro[indoline-3,4′-pyrano[2,3-c]chromene
derivatives were obtained in high yields (Table 3).
Proposed mechanism for the synthesis of spirooxindole
derivatives 4 and 5 was described in Scheme 2 [11, 20]. The
process represents a typical cascade reaction in which the
isatin 1 first condenses with methylene active compound 2 to
afford isatylidene malononitrile derivative 6 in the presence
of [Sipim]Cl in water. This step was regarded as a fast Kno-
evenagel condensation. Then, 6 is attacked via Michael addi-
tion of 1,3-dicarbonyl compound 3 to give the intermediate
1 3

J IRAN CHEM SOC
Table 2 continued
Ph
N
239-
241
238-
240
[14]
N
O
NH2
Me
H
Cl
COOEt
COOEt
COOEt
CN
60
90
75
25
30
80
75
80
91
88
6
7
COOEt
O
N
H
4f
Ph
N
246-
247
241-
242
[15]
N
O
NH2
Me
Cl
COOEt
O
N
H
4g
Ph
N
267-
269
265-
266
[15]
N
O
NH2
Me
NO2
8
O2N
COOEt
O
N
H
4h
Ph
N
224-
226
226-
227
[12]
N
O
NH2
CN
Me
9c
H
O
N
Me
4i
Ph
N
>270
288-
289
[12]
N
O
NH2
CN
Me
Me
CN
10
Me
O
N
H
4j
Reaction conditions: isatin (1 mmol), methylene active compound (1 mmol), 3-methyl-l-phenyl-5-pyrazolone (1 mmol), catalyst (0.05 g), water
(5 mL) at refluxing conditions
a
Isolated yield
b
1-Methyl-isatin was used instead of isatin
7 followed by the cycloaddition of hydroxyl group to the
cyano moiety to form the desired product 4 or 5 (Scheme 3).
The possibility of recycling the catalyst [Sipim]Cl was
examined using the reaction of isatin, malononitrile, and
3-methyl-l-phenyl-5-pyrazolone under the optimized con-
ditions. Upon completion, the reaction mixture was washed
with warm ethanol (3 × 5 cm3). The recovered catalyst was
dried and reused for subsequent runs. The recycled catalyst
was reused four times without any additional treatment. No
observation of any appreciable loss in the catalytic activity
of [Sipim]Cl was observed (Fig. 2).
Conclusions
In conclusion, this work shows that [Sipim]Cl which can be
prepared by simple operation from commercially available
and relative cheap starting materials, efficiently catalyzed the
1 3

J IRAN CHEM SOC
Table 3 Preparation
of spiro[indoline-3,4′-
O
O Si
O
pyrano[2,3-c]chromene]
derivatives catalyzed by [Sipim]
Cl in water at reflux conditions
N
SiO2
OH
O
NH
Cl
O
O
O
CN
Y
R
NH2
O
+
+
R
O
Y
H2O (Reflux)
N
O
O
N
H
H
5a-k
Entry
R
Y
Product
Time
(min)
Yield mp oC
(%)b
Lit.
mp
(oC)
>270
294-
296
[18]
O
O
NH2
CN
O
H
CN
CN
CN
20
90
1
2
3
4
5
O
N
H
5a
>270
>300
[20]
O
O
NH2
CN
O
Cl
20
20
45
60
85
Cl
O
N
H
5b
>270
-
O
O
NH2
CN
O
NO2
88
O2N
O
N
H
5c
>270
275-
277
[11]
O
O
NH2
COOMe
O
H
COOMe
COOMe
80
O
N
H
5d
>270
279-
281
[20]
O
O
NH2
O
Cl
75
Cl
COOMe
O
N
H
5e
1 3

J IRAN CHEM SOC
Table 3 continued
>270
>270
288-
290
O
O
[20]
NH2
O
Br
COOMe
60
50
60
90
90
75
70
80
83
80
75
80
6
7
Br
COOMe
O
N
H
5f
-
O
O
NH2
O
NO2 COOMe
O2N
COOMe
O
N
H
5g
253-
255
252-
254
[18]
O
O
NH2
COOEt
O
H
Cl
Br
COOEt
COOEt
COOEt
8
O
N
H
5h
>270
275-
277
[20]
O
O
NH2
COOEt
O
9
Cl
Br
O
N
H
5i
>270
280-
282
[20]
O
O
NH2
O
10
11
COOEt
O
N
H
5j
267-
268
-
Reaction conditions: isatin
(1 mmol), methylene active
compound (1 mmol),
O
O
NH2
O
NO2 COOEt
O2N
4-hydroxy-coumarin (1 mmol),
catalyst (0.05 g), water (5 mL)
at refluxing conditions
COOEt
O
N
H
a
Isolated yield
5k
1 3

J IRAN CHEM SOC
N
N
O
R
CN
H
O
O
N
CN
2
R
H
1
O
N
H
H
N
CN
OH2
NH
N
N
NC
R
O
N
H
-H2O
CN
NC
R
O
N
H
6
NH
N
NC
C
O
N
NH
R
N
OH
O
O
N
Ph
H
7
R
N
or
N
O
H
N
HN
Ph
N
CN
N
O
NH
O
O
H
NC
O
Ph
H
N
NH
N
R
R
N
N
N
HN
Ph
N
O
O
NC
NH
4 or 5 when 4-hydroxy coumarin used
NH2
O
O Si
SiO2
N
NH
N
Cl
O
Scheme 3 Proposed mechanism for the synthesis of spirooxindoles
1 3

J IRAN CHEM SOC
11. S.L. Zhu, S.J. Ji, Y. Zhang, Tetrahedron 63, 9365–9372 (2007)
12. M.N. Elinson, A.S. Dorofeev, F.M. Miloserdov, G.I. Nikishin,
Mol. Divers. 13, 47–52 (2009)
13. R. Sridhar, B. Srinivas, B. Madhav, V.P. Reddy, Y.V.D. Nageswar,
K.R. Rao, Can. J. Chem. 87, 1704–1707 (2009)
14. A. Dandia, A.K. Jain, D.S. Bhati, Synth. Commun. 41, 2905–
2919 (2011)
15. A. Dandia, V. Parewa, A.K. Jain, K.S. Rathore, Green Chem. 13,
2135–2145 (2011)
16. Y. Zou, Y. Hu, H. Liu, D. Shi, ACS Comb. Sci. 14, 38–43 (2012)
17. H.R. Safaei, M. Shekouhy, A. Shirinfeshan, S. Rahmanpur, Mol.
Divers. 16, 669–683 (2012)
18. P. Saluja, K. Aggarwal, J.M. Khurana, Synth. Commun. 43,
3239–3246 (2013)
19. A. Thakur, M. Tripathi, U.C. Rajesh, D.S. Rawat, RSC Adv. 3,
18142–18148 (2013)
20. G. Mohammadi Ziarani, N. Hosseini Mohtasham, N. Lashgari,
A. Badiei, M. Amanlou, R. Bazl, JNS 2, 489–500 (2013)
21. S.P. Satasia, P.N. Kalaria, J.R. Avalani, D.K. Raval, Tetrahedron
70, 5763–5767 (2014)
Fig. 2 Recyclability of [Sipim]Cl in the reaction of isatin (1 mmol),
malononitrile (1 mmol), 3-methyl-l-phenyl-5-pyrazolone (1 mmol),
and [Sipim]Cl (0.05 g) in water (5 mL) under reflux conditions. Reac-
tion time = 15 min
22. W. Liju, K. Ablajan, F. Jun, Ultrason. Sonochem. 22, 113–118
(2015)
23. K. Qiao, H. Hagiwara, C. Yokoyama, J. Mol. Catal. A: Chem.
synthesis of spirooxindoles. It could also be recovered and
reused for several times without noticeable loss of reactivity.
246, 65–69 (2006)
24. R. Sugimura, K. Qiao, D. Tomida, C. Yokoyama, Catal. Com-
mun. 8, 770–772 (2007)
25. A. Chrobok, S. Baj, W. Pudlo, A. Jarzebski, Appl. Catal. A Gen.
366, 22–28 (2009)
26. M.N. Sefat, D. Saberi, K. Niknam, Catal. Lett. 141, 1713–1720
(2011)
Acknowledgments We are thankful to Persian Gulf University
Research Council for partial support of this work. Also, we are thank-
ful to the School of Chemistry, Manchester University for running
NMRs.
27. M. Baghernejad, K. Niknam, Int. J. Chem. 4, 52–60 (2012)
28. K. Niknam, A. Piran, Green Sustain. Chem. 3(2A), 1–8 (2013)
29. F. Shirini, M. Seddighi, M. Mazloumi, M. Makhsous, M.
Abedini, J. Mol. Liq. 208, 291–297 (2015)
30. A.R. Moosavi-Zare, M.A. Zolfigol, M. Zarei, A. Zare, V.
Khakyzadeh, J. Mol. Liq. 211, 373–380 (2015)
31. M. Seddighi, F. Shirini, M. Mamaghani, C. R. Chim. 18, 573–
580 (2015)
32. K. Niknam, P. Abolpour, Monatsh. Chem. 146, 683–690 (2015)
33. K. Niknam, A. Jamali, M. Tajaddod, A. Deris, Chin. J. Catal. 33,
1312–1317 (2012)
34. K. Niknam, A. Jamali, Chin. J. Catal. 33, 1840–1849 (2012)
35. S.M.G. Ahmadi-Ana, M. Baghernejad, K. Niknam, Chin. J.
Chem. 30, 517–521 (2012)
References
1. C.C. Galliford, K.A. Scheidt, Angew. Chem. 119, 8902–8912
(2007) [C.C. Galliford, K.A. Scheidt, Angew. Chem. Int. Ed. 46,
8748–8758 (2007)]
2. K. Ding, Y.P. Lu, N. Coleska, J. Med. Chem. 49, 3432–3435
(2006)
3. B. Yu, D.Q. Yu, H.M. Liu, Eur. J. Med. Chem. 97, 673–698
(2015)
4. J.P. Nandy, M. Prakesch, S. Khadem, P.T. Reddy, U. Sharma, P.
Arya, Chem. Rev. 109, 1999–2060 (2009)
5. M. Pettersson, D. Knueppel, S.F. Martin, Org. Lett. 9, 4623–
4626 (2007)
36. K. Niknam, N. Borazjani, R. Rashidian, A. Jamali, Chin. J.
6. C. Marti, E.M. Carreira, Eur. J. Org. Chem. (12), 2209–2219
(2003)
7. C.V. Galliford, J.A. Martenson, C. Stern, K.A. Scheidt, Chem.
Commun. (6), 631–633 (2007)
Catal. 34, 2245–2254 (2013)
37. K. Niknam, R. Rashidian, A. Jamali, Sci. Iran. C 20, 1863–1870
(2013)
38. K. Niknam, M. Sadeghi Habibabad, A. Deris, N. Aeinjamshid,
Monatsh. Chem. 144, 987–992 (2013)
39. K. Niknam, S. Mojikhalifeh, Mol. Diver. 18, 111–117 (2014)
40. K. Niknam, N. Borazjani, Monatsh. Chem. (2015). doi:10.1007/
s00706-015-1552-2
8. B. Liang, S. Kalidindi, J.A. Porco Jr, C.R.J. Stephenson, Org.
Lett. 12, 572–575 (2010)
9. R.G. Redkin, L.A. Shemchuk, V.P. Chernykh, O.V. Shishkin,
S.V. Shishkin, Tetrahedron 63, 11444–11450 (2007)
10. A. Dandia, R. Singh, P. Sarawgi, S. Khaturia, Chin. J. Chem. 24,
950–954 (2006)
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