Heterogeneous AlPO4(SO3H) nanosheets: novel catalyst for the multi-component synthesis of quinazolinones and highly functionalized piperidines

Article abstract of DOI:10.1007/s13738-018-1308-0

Abstract: Nanosheets AlPO₄(SO₃H) as a highly active solid acid catalyst were prepared and characterized. The morphology of obtained catalyst exhibited nanosheets with?～?25–35?nm thickness. The heterogeneous nanocatalyst was characterized by FT-IR, EDX, and FE-SEM analysis. The nanosulfonated-AlPO₄ were found useful for cyclization synthesis of highly functionalized piperidines and quinazolinones derivatives in good to excellent yields. Notable features include easy and quick isolation of products, ease of handling of the catalyst at low cost, no need to purify with column chromatography, and mild reaction conditions. In addition, according to the literature, another significant feature of our method for quinazolinone synthesis is that structurally diverse molecules were synthesized. Finally, the newly developed catalytic systems avoid the use of toxic metal catalysts and were reused up to 5 times without a noticeable their catalytic activity.

Full text of DOI:10.1007/s13738-018-1308-0

Journal of the Iranian Chemical Society
https://doi.org/10.1007/s13738-018-1308-0
ORIGINAL PAPER
Heterogeneous AlPO4(SO3H) nanosheets: novel catalyst
for the multi‑component synthesis of quinazolinones and highly
functionalized piperidines
Hashem Sharghi1 · Jasem Aboonajmi1 · Mahdi Aberi1 · Pezhman Shiri1
Received: 2 December 2017 / Accepted: 17 January 2018
© Iranian Chemical Society 2018
Abstract
Nanosheets AlPO4(SO3H) as a highly active solid acid catalyst were prepared and characterized. The morphology of obtained
catalyst exhibited nanosheets with ∼ 25–35 nm thickness. The heterogeneous nanocatalyst was characterized by FT-IR,
EDX, and FE-SEM analysis. The nanosulfonated-AlPO4 were found useful for cyclization synthesis of highly functionalized
piperidines and quinazolinones derivatives in good to excellent yields. Notable features include easy and quick isolation
of products, ease of handling of the catalyst at low cost, no need to purify with column chromatography, and mild reaction
conditions. In addition, according to the literature, another signifcant feature of our method for quinazolinone synthesis is
that structurally diverse molecules were synthesized. Finally, the newly developed catalytic systems avoid the use of toxic
metal catalysts and were reused up to 5 times without a noticeable their catalytic activity.
Electronic supplementary material The online version of this
article (https://doi.org/10.1007/s13738-018-1308-0) contains
supplementary material, which is available to authorized users.
* Hashem Sharghi
shashem@susc.ac.ir
1
Department of Chemistry, Shiraz University, Shiraz 71454,
Islamic Republic of Iran
Vol.:(0123456789)
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Journal of the Iranian Chemical Society
Graphical Abstract
Keywords Nanosheets AlPO4(SO3H) · Heterogeneous catalysis · Multi-component reactions · Quinazolinone · Piperidine
general environmental friendliness, and enabling straightfor-
ward access to large libraries of drug-like compounds [2–7].
Investigation on this topic is attractive in organic synthesis
owing to their values in preparation of diverse heterocy-
clic molecules which may be efficient in drug discovery
procedures.
Introduction
Homogeneous acids are the most frequently catalysts used
in organic reactions. They are soluble in the reaction mix-
ture which increases production costs. They cannot be com-
pletely washed out from the biodiesel, as well. Immobiliza-
tion of homogeneous acid on solid materials is the best way
to be easily separated from the reaction mixture. Recently,
functionalized separable AlPO4 nanocomposite materials
have emerged as relatively new class and viable alternatives
to conventional materials for organic transformations on
account of their stability and large specifc surface area [1].
Nonetheless, modifcation and functionalization of this sup-
port are less used and should be investigated more.
Based on these contexts, the development of simple syn-
thetic ways for N-heterocycles from ready substances is a
critical task in organic reactions. Quinazolinone [8–10] and
piperidine [11–14] ring systems are heterocyclic motif found
in natural products and key units in pharmaceuticals. Some
new methodologies have been investigated for their synthesis
[8–19]. Based on our previous studies [20–24], which focus on
the synthesis of new catalysts for multi-component reactions
under mild conditions, herein, we wish to report AlPO4(SO3H)
nanosheets as a new, efficient, and reusable catalyst for
In recent decades, research interests have been devoted
toward new methodologies in one-pot multi-component reac-
tions (MCRs) for reasons of energy efciency, atom economy,
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Journal of the Iranian Chemical Society
performing multi-component reaction toward quinazolinone
and piperidine derivatives.
6,6‑Dimethyl‑9‑phenyl‑5,6,7,9‑tetrahydro‑[1,2,4]
triazolo[5,1‑b]quinazolin‑8(4H)‑one (4a) White solid; 95%
yield; mp 248–250 °C; FT-IR (KBr cm−1): 3224, 3085,
1
2965, 1651, 1573, 1365, 1257, 732; H NMR (250 MHz,
Experimental section
CDCl3) δ (ppm): 1.03, 1.09 (2s, 6H, 2CH3), 2.22 (s, 2H,
CH2), 2.51 (s, 2H, CH2), 6.38 (s, 1H, CH), 7.15–7.26 (m,
5H, ArH), 7.60 (s, 1H, =CH), 11.76 (s, 1H, NH); 13C NMR
(62.9 MHz, CDCl3) δ (ppm): 27.6, 29.0, 32.8, 40.7, 50.4,
58.8, 107.4, 127.1, 128.3, 128.6, 140.6, 147.4, 148.5, 149.0,
193.8.
Instrumentation, analyses, and starting material
Chemical materials and solvents were purchased from Fluka,
Sigma-Aldrich, and Merck Companies and used without fur-
ther purifcation. NMR spectra were recorded in DMSO-d6
or CDCl3 solvents on a Bruker Avance DPX-250 (1H NMR
250 MHz and 13C NMR 62.9 MHz) spectrometer. IR spectra
were obtained using a Shimadzu FT-IR 8300 spectropho-
tometer. Characterization and surface morphology of the
nanocatalyst were performed with a MIRA3 TESCAN SEM,
operating at 20.0 kV. The energy-dispersive X-ray (EDX)
analysis was done using SIRIUS SD EDX analyzer. By a
Büchi-535 circulating oil melting point apparatus, melting
points were obtained in open capillary tubes.
6,6‑Dimethyl‑9‑(p‑tolyl)‑5,6,7,9‑tetrahydro‑[1,2,4]
triazolo[5,1‑b]quinazolin‑8(4H)‑one (4b) Pale yellow solid;
93% yield; mp 265–267 °C; FT-IR (KBr cm−1): 3240, 3085,
1
2923, 1651, 1581, 1365, 1249, 735; H NMR (250 MHz,
DMSO-d6) δ (ppm): 0.94, 1.02 (2s, 6H, 2CH3), 2.01–2.23
(m, 5H, CH2 and CH3), 2.44–2.59 (m, 2H, CH2), 6.14 (s,
1H, CH), 7.05 (s, 4H, ArH), 7.65 (s, 1H, =CH), 11.07 (s,
1H, NH); 13C NMR (62.9 MHz, DMSO-d6) δ (ppm): 20.56,
26.73, 28.47, 32.12, 49.75, 57.60, 105.67, 126.78, 128.72,
136.89, 138.73, 146.76, 149.90, 150.16, 192.85.
General procedure for the synthesis
of 6,6‑dimethyl‑9‑phenyl‑5,6,7,9‑tetrahydro‑[1,2,4]
triazolo[5,1‑b]quinazolin‑8(4H)‑one (4a–s)
9‑(4‑Chlorophenyl)‑6,6‑dimethyl‑5,6,7,9‑tetrahydro‑[1,2,4]
triazolo[5,1‑b]quinazolin‑8(4H)‑one (4c) Pale yellow solid;
93% yield; mp 304–306 °C; FT-IR (KBr cm−1): 3085,
1
2970, 1651, 1573, 1365, 1257, 763; H NMR (250 MHz,
A mixture of aldehyde (1.0 mmol), dimedone (1.0 mmol),
1H-1,2,4-triazol-3-amine (1.0 mmol) and nano-
AlPO4(SO3H) (0.1 g) was stirred in the acetonitrile (4.0 mL)
at 50 °C for an appropriate time. After the completion of the
reaction as indicated by TLC, dichloromethane was added
to the solidifed mixture and the insoluble catalyst was sepa-
rated by centrifugation. Evaporation of the solvent from the
fltrate and recrystallization of the solid residue from hot eth-
anol aforded the pure products in good to excellent yields.
DMSO-d6) δ (ppm): 0.70, 0.77 (2s, 6H, 2CH3), 1.89 (q, 2H,
J = 17.5 Hz, CH2), 2.26 (d, 2H, J = 10.0 Hz, CH2), 5.97
(s, 1H, CH), 6.96 (d, 2H, J = 7.5 Hz, ArH), 7.08 (d, 2H,
J = 7.5 Hz, ArH), 7.44 (s, 1H, =CH), 10.90 (s, 1H, NH); 13
C
NMR (62.9 MHz, DMSO-d6) δ (ppm): 26.84, 28.33, 32.13,
49.70, 57.33, 99.48, 105.15, 128.20, 128.82, 132.24, 140.45,
146.74, 150.12, 150.49, 192.91.
9‑(4‑Methoxyphenyl)‑6,6‑dimethyl‑5,6,7,9‑tetrahy‑
dro‑[1,2,4]triazolo[5,1‑b]quinazolin‑8(4H)‑one (4d) Pale
yellow solid; 90% yield; mp 229–231 °C; FT-IR (KBr cm−1):
3085, 2923, 1651, 1573, 1365, 1249; 1H NMR (250 MHz,
DMSO-d6) δ (ppm): 0.95, 1.02 (2s, 6H, 2CH3), 2.05 (d, 1H,
J = 15.0 Hz), 2.20 (d, 1H, J = 15.0 Hz), 2.48–2.52 (m, 2H,
CH2), 3.67 (s, 3H, OCH3), 6.14 (s, 1H, CH), 6.81 (d, 2H,
J = 10.0 Hz, ArH), 7.09 (d, 2H, J = 10.0 Hz, ArH), 7.65
(s, 1H, =CH), 11.07 (s, 1H, NH); 13C NMR (62.9 MHz,
DMSO-d6) δ (ppm): 26.77, 28.47, 32.11, 49.76, 54.96,
57.29, 105.70, 113.51, 128.06, 133.80, 146.70, 149.88,
150.10, 158.63, 192.89.
General procedure for the synthesis of highly
functionalized piperidines (8a–l)
A solution of aromatic amine (2.0 mmol) and alkyl acetoac-
etate (1.0 mmol) in EtOH (5.0 mL) stirred for 20 min in the
presence of nano-AlPO4(SO3H) (0.15 g) at room tempera-
ture. Next, the aromatic aldehyde (2.0 mmol) was added and
the reaction mixture was stirred for the time indicated in
Table 4. After the completion of the reaction, as indicated
by TLC, the solid material was fltered of, dried, and then
dissolved in CH2Cl2 (10 mL). The nano-AlPO4(SO3H) was
recovered by centrifuging, and the solvent was evaporated
under vacuum. The obtained solid was washed with EtOH
to give the pure product.
9‑(4‑Isopropylphenyl)‑6,6‑dimethyl‑5,6,7,9‑tetrahy‑
dro‑[1,2,4]triazolo[5,1‑b]quinazolin‑8(4H)‑one (4e) White
solid; 93% yield; mp 283–284 °C; FT-IR (KBr cm−1):
3247, 3085, 2962, 1651, 1581, 1365, 1249, 732; 1H NMR
(250 MHz, DMSO-d6) δ (ppm): 0.95, 1.01 (2s, 6H, 2CH3),
1.11 (d, 6H, J = 5 Hz, 2CH3), 2.05 (d, 1H, J = 17.5 Hz),
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Journal of the Iranian Chemical Society
2.19 (d, 1H, J = 15.0 Hz), 2.51 (s, 2H, CH2), 2.69–2.85 (m,
1H, CH), 6.14 (s, 1H, CH), 7.06–7.11 (m, 4H, ArH), 7.64
(s, 1H, =CH), 11.09 (s, 1H, NH); 13C NMR (62.9 MHz,
DMSO-d6) δ (ppm): 23.66, 23.73, 26.89, 28.39, 32.13,
32.99, 49.75, 57.59, 105.55, 126.10, 126.86, 139.03, 146.71,
147.70, 149.90, 150.28, 192.89.
29.02, 32.82, 50.53, 54.16, 56.18, 60.44, 106.08, 112.96,
120.95, 124.08, 135.18, 147.03, 147.51, 150.28, 151.16,
152.88, 193.41.
9‑(3‑Bromophenyl)‑6,6‑dimethyl‑5,6,7,9‑tetrahydro‑[1,2,4]
triazolo[5,1‑b]quinazolin‑8(4H)‑one (4j) Pale yellow solid;
90% yield; mp 281–283 °C; FT-IR (KBr cm−1): 3209, 3070,
1
6,6‑Dimethyl‑9‑(4‑nitrophenyl)‑5,6,7,9‑tetrahydro‑[1,2,4]
triazolo[5,1‑b]quinazolin‑8(4H)‑one (4f) Yellow solid; 94%
yield; 290–291 °C; FT-IR (KBr cm−1): 3085, 2947, 1643,
1573, 1350, 1249, 732; 1H NMR (250 MHz, DMSO-d6) δ
(ppm): 0.93, 1.02 (2s, 6H, 2CH3), 2.13 (q, 2H, J = 17.5 Hz,
CH2), 2.50 (d, 2H, J = 12.5 Hz, CH2), 6.35 (s, 1H, CH), 7.46
(d, 2H, J = 7.5 Hz, ArH), 7.71 (s, 1H, =CH), 8.13 (d, 2H,
J = 7.5 Hz, ArH), 11.30 (s, 1H, NH); 13C NMR (62.9 MHz,
DMSO-d6) δ (ppm): 26.90, 28.25, 32.18, 49.62, 57.48,
104.69, 123.51, 128.42, 146.78, 146.87, 148.35, 150.37,
150.94, 192.96.
2935, 1643, 1573, 1365, 1257, 725; H NMR (250 MHz,
DMSO-d6) δ (ppm): 1.71, 1.78 (2s, 6H, 2CH3), 2.91 (q, 2H,
J = 15.0, CH2), 3.23–3.25 (m, 2H, CH2), 6.97 (s, 1H, CH),
7.89 -8.03 (m, 2H, ArH), 8.16–8.19 (m, 2H, ArH), 8.46
(s, 1H, =CH), 11.96 (s, 1H, NH); 13C NMR (62.9 MHz,
DMSO-d6) δ (ppm): 25.71, 27.20, 31.08, 48.57, 56.30,
103.78, 120.27, 124.82, 128.79, 129.44, 142.88, 145.59,
149.09, 149.64, 191.86.
6,6‑Dimethyl‑9‑(3‑nitrophenyl)‑5,6,7,9‑tetrahydro‑[1,2,4]
triazolo[5,1‑b]quinazolin‑8(4H)‑one (4k) Yellow solid; 94%
yield; mp 266–268 °C; FT-IR (KBr cm-1): 3075, 2930, 1643,
1527, 1350, 1257, 732; 1H NMR (250 MHz, DMSO-d6) δ
(ppm): 0.96, 1.03 (2s, 6H, 2CH3), 2.07 (d, 1H, J = 17.5 Hz),
2.07 (d, 1H, J = 17.5 Hz), 2.56 (s, 2H, CH2), 6.40 (s, 1H,
CH), 7.55–7.67 (m, 2H, ArH), 7.72 (s, 1H, =CH), 8.04–8.12
(m, 2H, ArH), 11.30 (s, 1H, NH); 13C NMR (62.9 MHz,
DMSO-d6) δ (ppm): 26.82, 28.30, 32.19, 49.62, 57.37,
104.56, 121.64, 122.76, 129.99, 133.67, 143.41, 146.72,
147.53, 150.38, 151.08, 193.04.
9‑(4‑Fluorophenyl)‑6,6‑dimethyl‑5,6,7,9‑tetrahydro‑[1,2,4]
triazolo[5,1‑b]quinazolin‑8(4H)‑one (4g) Pale yellow solid;
90% yield; mp 258–260 °C; FT-IR (KBr cm−1): 3132,
1
2954, 1651, 1581, 1365, 1218, 763; H NMR (250 MHz,
DMSO-d6) δ (ppm): 0.94, 1.02 (2s, 6H, 2CH3), 2.13 (q, 2H,
J = 17.5 Hz, CH2), 2.52 (s, 2H, CH2), 6.21 (s, 1H, CH),
7.05–7.12 (m, 2H, ArH), 7.19–7.25 (m, 2H, ArH), 7.68
(s, 1H, =CH), 11.15 (s, 1H, NH); 13C NMR (62.9 MHz,
DMSO-d6) δ (ppm): 26.84, 28.35, 32.13, 49.71, 57.22,
105.34, 114.81, 115.15, 128.88, 129.01, 137.78, 137.82,
146.72, 150.07, 150.39, 159.49, 163.37, 192.92.
6,6‑Dimethyl‑9‑(naphthalen‑1‑yl)‑5,6,7,9‑tetrahydro‑[1,2,4]
triazolo[5,1‑b]quinazolin‑8(4H)‑one (4l) Light yellow
solid; 85% yield; mp 299–300 °C; FT-IR (KBr cm-1): 3078,
1
9‑(4‑(Dimethylamino)phenyl)‑6,6‑dimethyl‑5,6,7,9‑tetrahy‑
dro‑[1,2,4]triazolo[5,1‑b]quinazolin‑8(4H)‑one (4h) Pale
yellow solid; 90% yield; mp 287–289 °C; FT-IR (KBr cm−1):
3247, 3085, 2923, 1651, 1581, 1365, 1257, 732; 1H NMR
(250 MHz, DMSO-d6) δ (ppm): 0.96, 1.02 (2s, 6H, 2CH3),
2.04 (d, 1H, J = 15 Hz), 2.20 (d, 1H, J = 15.0 Hz), 2.55 (d,
2H, J = 15 Hz, CH2), 2.80, 2.81 (2s, 6H, 2 N–CH3), 6.07
(s, 1H, CH), 6.57 (d, 2H, J = 7.5 Hz, ArH), 6.97 (d, 2H,
2923, 1643, 1573, 1365, 1249, 779; H NMR (250 MHz,
DMSO-d6) δ (ppm): 1.01, 1.05 (2s, 6H, 2CH3), 2.04 (d,
1H, J = 17.5 Hz), 2.20 (d, 1H, J = 17.5 Hz), 2.61 (s, 2H,
CH2), 7.09 (s, 1H, CH), 7.32–7.43 (m, 2H, ArH), 7.49–7.63
(m, 3H, ArH), 7.80 (d, 1H, J = 7.5, ArH), 7.90 (d, 1H,
J = 7.5 Hz, ArH), 8.53 (s, 1H, =CH), 11.22 (s, 1H, NH); 13
C
NMR (62.9 MHz, DMSO-d6) δ (ppm): 27.05, 28.42, 32.17,
49.78, 106.02, 123.80, 125.34, 125.67, 126.13, 128.25,
128.33, 130.70, 133.17, 138.27, 146.45, 149.72, 150.67,
193.03.
J = 7.5 Hz, ArH), 7.62 (s, 1H, =CH), 10.99 (s, 1H, NH); 13
C
NMR (62.9 MHz, DMSO-d6) δ (ppm): 26.74, 28.59, 32.09,
40.00, 49.81, 57.34, 105.96, 111.83, 127.53, 129.33, 146.69,
149.71, 149.84, 192.88.
9‑(2‑Chlorophenyl)‑6,6‑dimethyl‑5,6,7,9‑tetrahydro‑[1,2,4]
triazolo[5,1‑b]quinazolin‑8(4H)‑one (4m) Pale yellow solid;
89% yield; mp 288–290 °C; FT-IR (KBr cm-1): 3224, 3085,
9‑(2,3‑Dimethoxyphenyl)‑6,6‑dimethyl‑5,6,7,9‑tetrahy‑
dro‑[1,2,4]triazolo[5,1‑b]quinazolin‑8(4H)‑one (4i) White
solid; 89% yield; mp 226–228 °C; FT-IR (KBr cm−1): 3085,
1
2923, 1643, 1573, 1365, 1257, 748; H NMR (250 MHz,
DMSO-d6) δ (ppm): 0.97, 1.02 (2s, 6H, 2CH3), 2.04–2.05
(m, 1H), 2.19 (d, 1H, J = 17.5 Hz), 2.51–2.60 (m, 2H,
CH2), 6.55 (s, 1H, CH), 7.21–7.36 (m, 4H, ArH), 7.65
(s, 1H, =CH), 11.20 (s, 1H, NH); 13C NMR (62.9 MHz,
DMSO-d6) δ (ppm): 25.66, 27.38, 30.95, 48.62, 55.23,
103.38, 116.89, 125.99, 128.26, 128.43, 137.05, 145.72,
148.91, 149.90, 191.71.
1
2931, 1643, 1581, 1365, 1257, 748; H NMR (250 MHz,
DMSO-d6) δ (ppm): 0.96, 1.02 (2s, 6H, 2CH3), 2.09 (q, 2H,
J = 17.5 Hz, CH2), 2.48–2.57 (m, 2H, CH2), 3.69, 3.74 (2s,
6H, 2OCH3), 6.43 (s, 1H, CH), 6.69–6.73 (m, 1H, ArH),
6.86–6.96 (m, 2H, ArH), 7.61 (s, 1H, =CH), 11.04 (s, 1H,
NH); 13C NMR (62.9 MHz, DMSO-d6) δ (ppm): 27.57,
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Journal of the Iranian Chemical Society
2500
O Kα
a
P Kα
AlKα
2000
1500
1000
500
0
S Kβ
S Kα
P Kβ
keV
0
5
10
b
c
Fig. 1 a Energy-dispersive x-ray spectroscopy (EDX) of the AlPO4(SO3H) nanosheets, b low magnifcation FE-SEM image of AlPO4(SO3H)
nanosheets, c high-magnifcation FE-SEM image of AlPO4(SO3H) nanosheets
6,6‑Dimethyl‑9‑(o‑tolyl)‑5,6,7,9‑tetrahydro‑[1,2,4]
triazolo[5,1‑b]quinazolin‑8(4H)‑one (4n) White solid; 93%
yield; mp 299–300 °C; FT-IR (KBr cm-1): 3085, 2925, 1643,
1581, 1365, 1257, 748; 1H NMR (250 MHz, DMSO-d6) δ
(ppm): 0.97, 1.03 (2s, 6H, 2CH3), 2.12 (q, 2H, J = 17.5 Hz,
CH2), 2.48–2.60 (m, 5H, CH3 and CH2), 6.42 (s, 1H, CH),
6.95–7.09 (m, 4H, ArH), 7.63 (s, 1H, =CH), 11.09 (s, 1H,
NH); 13C NMR (62.9 MHz, DMSO-d6) δ (ppm): 18.89,
26.83, 28.48, 32.18, 49.73, 54.12, 106.14, 126.18, 126.64,
127.43, 129.96, 135.56, 140.32, 146.55, 149.87, 150.42,
193.00.
1573, 1365, 1257, 748; 1H NMR (250 MHz, DMSO-d6) δ
(ppm): 0.98, 1.03 (2s, 6H, 2CH3), 2.03 (m, 1H), 2.19 (d,
1H, J = 15.0 Hz), 2.49–2.60 (m, 2H, CH2), 6.56 (s, 1H,
CH), 7.10–7.16 (m, 1H, ArH), 7.25–7.30 (m, 2H, ArH),
7.52 (d, 1H, J = 7.5 Hz, ArH), 7.64 (s, 1H, =CH), 11.21 (s,
1H, NH); 13C NMR (62.9 MHz, DMSO-d6) δ (ppm): 25.82,
27.32, 30.96, 48.63, 103.68, 116.88, 121.41, 126.64, 128.47,
131.66, 138.75, 145.61, 148.92, 149.86, 191.71.
9‑(4‑Hydroxyphenyl)‑6,6‑dimethyl‑5,6,7,9‑tetrahydro‑[1,2,4]
triazolo[5,1‑b]quinazolin‑8(4H)‑one (4p) Pale yellow solid;
89% yield; mp 305–307 °C; FT-IR (KBr cm-1): 3209, 3085,
1
9‑(2‑Bromophenyl)‑6,6‑dimethyl‑5,6,7,9‑tetrahydro‑[1,2,4]
triazolo[5,1‑b]quinazolin‑8(4H)‑one (4o) White solid; 90%
yield; mp 278–280 °C; FT-IR (KBr cm-1): 3085, 29231648,
2931, 1635, 1573, 1365, 1257, 732; H NMR (250 MHz,
DMSO-d6) δ (ppm): 0.95, 1.01 (2s, 6H, 2CH3), 2.13 (q,
2H, J = 17.5 Hz, CH2), 2.46 (d, 1H, 17.5 Hz), 2.54 (d, 1H,
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Journal of the Iranian Chemical Society
Table 1 Optimization studies on one-pot three-component reaction of benzaldehyde (1a), dimedone (2), and 1H-1,2,4-triazol-3-amine (3) for
synthesis of (4a) in the presence of AlPO4(SO3H) nanosheets
Entry
Solvent
Temperature (°C)
Catalyst (g)
Time (min)
Yield (%)a
1
2
3
4
5
6
7
8
Acetonitrile
Acetonitrile
Acetonitrile
Acetonitrile
Acetonitrile
Ethanol
Methanol
–
Water
Acetonitrile
Acetonitrile
Acetonitrile
Acetonitrile
Acetonitrile
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
50
Refux
AlPO4 (0.3 g)
Amino-functionalized AlPO4 (0.3 g)
CuFe2O4 (0.3 g)
180
180
180
180
30
30
30
180
30
30
30
30
30
30
24
58
88
59
48
5
49
92
95
80
95
95
p-Dodecylbenzenesulfonic acid (0.3 g)
Sulfonated AlPO4 (0.3 g)
Sulfonated AlPO4 (0.3 g)
Sulfonated AlPO4 (0.3 g)
Sulfonated AlPO4 (0.3 g)
Sulfonated AlPO4 (0.3 g)
Sulfonated AlPO4 (0.2 g)
Sulfonated AlPO4 (0.1 g)
Sulfonated AlPO4 (0.05 g)
Sulfonated AlPO4 (0.1 g)
Sulfonated AlPO4 (0.1 g)
9
10
11
12
13
14
10
10
All reactions were carried out using 1a (1.0 mmol), 2 (1.0 mmol), 3 (1.0 mmol), and the catalyst (0.1 g) in solvent (4.0 mL) under air atmosphere
aYield of the isolated product
17.5 Hz), 6.09 (s, 1H, CH), 6.63 (d, 2H, J = 7.5 Hz, ArH),
6.98 (d, 2H, J = 7.5 Hz, ArH), 7.65 (s, 1H, =CH), 9.39 (s,
1H, OH), 11.03 (s, 1H, NH); 13C NMR (62.9 MHz, DMSO-
d6) δ (ppm): 25.66, 27.40, 30.99, 48.69, 56.23, 104.75,
113.73, 126.95, 131.09, 145.58, 148.68, 148.88, 155.74,
191.78.
J = 17.5, CH2), 2.56 (s, 2H, CH2), 6.37 (s, 1H, CH), 7.25
(d, 1H, J = 10 Hz, ArH), 7.45–7.48 (m, 2H, ArH), 7.68 (s,
1H, =CH), 7.79–7.89 (m, 4H, ArH), 11.19 (s, 1H, NH);
13C NMR (62.9 MHz, DMSO-d6) δ (ppm): 26.74, 28.45,
32.15, 49.76, 58.20, 105.39, 124.64, 126.05, 126.12, 126.28,
127.36, 127.87, 128.07, 132.39, 132.45, 138.80, 146.80,
150.08, 150.48, 171.96, 192.98.
9‑(3,4‑Dimethoxyphenyl)‑6,6‑dimethyl‑5,6,7,9‑tetrahy‑
dro‑[1,2,4]triazolo[5,1‑b]quinazolin‑8(4H)‑one (4q) White
solid; 85% yield; mp 219–220 °C; FT-IR (KBr cm-1): 3078,
6,6‑Dimethyl‑9‑(2‑oxo‑1,2‑dihydroquinolin‑3‑yl)‑5,6,7,9‑tet‑
rahydro‑[1,2,4]triazolo[5,1‑b]quinazolin‑8(4H)‑one
(4s) White solid; 85% yield; mp > 300 °C; FT-IR (KBr
cm-1): 3278, 3085, 2930, 1658, 1620, 1566, 1357, 1257,
7565; 1H NMR (250 MHz, DMSO-d6) δ (ppm): 0.94, 1.02
(2s, 6H, 2CH3), 2.00 (d, 1H, J = 15.0 Hz), 2.20 (d, 1H,
J = 15.0 Hz), 2.38 (d, 1H, J = 17.5 Hz), 2.57 (s, 1H), 6.20
(s, 1H, CH), 7.12–7.24 (m, 2H, ArH), 7.42–7.48 (m, 1H,
ArH),7.62 (s, 1H, ArH), 7.70 (d, 1H, J = 7.5 Hz, ArH),
7.98 (s, 1H, =CH), 11.03 (s, 1H, NH), 11.57 (s, 1H, NH);
13C NMR (62.9 MHz, DMSO-d6) δ (ppm): 26.28, 28.76,
32.09, 49.94, 56.32, 103.03, 114.60, 118.58, 121.77, 128.09,
130.24, 138.45, 149.49, 151.75, 160.00, 192.83.
1
2931, 1651, 1581, 1365, 1257, 740; H NMR (250 MHz,
DMSO-d6) δ (ppm): 0.98, 1.02 (2s, 6H, 2CH3), 2.06 (d, 1H,
J = 17.5 Hz), 2.21 (d, 1H, J = 17.5 Hz), 2.49–2.61 (m, 2H,
CH2), 3.67 (s, 6H, 2OCH3), 6.15 (s, 1H, CH), 6.64–6.69
(m, 1H, ArH), 6.80–6.84 (m, 2H, ArH), 7.67 (s, 1H, =CH),
11.05 (s, 1H, NH); 13C NMR (62.9 MHz, DMSO-d6) δ
(ppm): 25.52, 27.54, 31.00, 48.70, 54.29, 56.47, 104.54,
109.84, 110.38, 117.97, 133.05, 145.60, 147.22, 148.79,
149.17, 170.92, 191.88.
6,6‑Dimethyl‑9‑(naphthalen‑2‑yl)‑5,6,7,9‑tetrahydro‑[1,2,4]
triazolo[5,1‑b]quinazolin‑8(4H)‑one (4r) White solid;
87% yield; mp 266–268 °C; FT-IR (KBr cm-1): 3085,
Methyl (2R,6S)‑1‑phenyl‑4‑(phenylamino)‑2,6‑di‑p‑tolyl‑1,
2,5,6‑tetrahydropyridine‑3‑carboxylate (8a) White solid;
94% yield; mp 220–221 °C; FT-IR (KBr cm-1): 694, 748,
1
2923, 1651, 1573, 1365, 1249, 756; H NMR (250 MHz,
DMSO-d6) δ (ppm): 0.95, 1.03 (2s, 6H, 2CH3), 2.13 (q, 2H,
1 3

Journal of the Iranian Chemical Society
Table 2 Synthesis of quinazolinone derivatives
Isolated yield
1072, 1188, 1257, 1319, 1373, 1442, 1504, 1589, 1658,
2862, 2947, 3016, 3232 cm−1; 1H NMR (250 MHz, CDCl3)
δ (ppm): 2.35 (s, 3H, CH3), 2.37 (s, 3H, CH3), 2.79 (dd,
J = 15.0, 2.5 Hz, 1H, H′-5), 2.91 (dd, J = 15.0, 5.0 Hz, 1H,
H″-5), 3.95 (s, 3H, OCH3), 5.13–5.16 (m, 1H, H-6), 6.31–
6.35 (m, 2H, ArH), 6.44 (s, 1H, H-2), 6.56 (d, J = 7.5 Hz,
2H, ArH), 6.62 (t, J = 7.5 Hz, 1H, ArH), 7.06–7.13 (m, 11H,
ArH), 7.24 (d, J = 10.0 Hz, 2H, ArH), 10.29 (s, 1H, NH);
13C NMR (62.9 MHz, CDCl3) δ (ppm): 21.16, 21.24, 33.78,
51.09, 55.04, 58.03, 98.24, 113.01, 116.14, 125.73, 125.86,
126.43, 126.66, 128.92, 128.96, 129.06, 129.38, 135.86,
136.68, 138.03, 139.80, 141.06, 147.15, 156.36, 168.68.
Ethyl (2R,6S)‑1‑(4‑chlorophenyl)‑4‑((4‑chlorophenyl)
amino)‑2,6‑diphenyl‑1,2,5,6‑tetrahydropyridine‑3‑carbox‑
ylate (8g) Pale yellow solid; 89% yield; mp 201–203 °C;
FT-IR (KBr cm−1): 1H NMR (250 MHz, CDCl3) δ (ppm):
1.50 (t, J = 7.5 Hz, 3H, OCH2CH3), 2.72 (dd, J = 15.0,
1 3

Journal of the Iranian Chemical Society
Scheme 1 Suggested mechanism for the synthesis of quinazolinone derivatives using nano-AlPO4(SO3H)
2.5 Hz, 1H, H′-5), 2.84–2.94 (m, 1H, H″-5), 4.34–4.41 (m,
1H, OCHaHb), 4.45–4.55 (m, 1H, OCHaHb), 5.13 (s, 1H,
H-6), 6.17–6.22 (m, 2H, ArH), 6.44–6.49 (m, 3H, H-2 and
ArH), 6.70–7.32 (m, 14H, ArH), 10.28 (s, 1H, NH); 13C
NMR (62.9 MHz, CDCl3) δ (ppm): 14.83, 33.51, 55.30,
58.34, 59.95, 98.76, 114.06, 121.24, 126.32, 126.52, 126.59,
127.02, 127.48, 128.41, 128.75, 128.83, 129.02, 131.34,
136.45, 142.28, 143.30, 145.53, 155.40, 168.14.
(KBr cm-1): 694, 756, 1033, 1072, 1180, 1249, 1373, 1450,
1504, 1596, 1651, 2839, 2954, 3232, 3448 cm−1; 1H NMR
(250 MHz, CDCl3) δ (ppm): 2.78 (dd, J = 15.0, 2.5 Hz, 1H,
H′-5), 2.89 (dd, J = 15.0, 5.0 Hz, 1H, H″-5), 3.80 (s, 3H,
OCH3), 3.81 (s, 3H, OCH3), 3.95 (s, 3H, OCH3), 5.10–5.13
(m, 1H, H-2), 6.36–6.41 (m, 5H, H-2 and ArH), 6.56 (d,
J = 7.5 Hz, 2H, ArH), 6.63 (t, J = 7.5 Hz, 1H, ArH), 6.86 (d,
J = 10.0 Hz, 4H, ArH), 7.06–7.15 (m, 7H, ArH), 7.23–7.27
(m, 2H, ArH), 10.31 (s, 1H, NH); 13C NMR (62.9 MHz,
CDCl3) δ (ppm): 33.83, 51.08, 54.65, 55.25, 55.32, 57.56,
98.23, 113.03, 113.68, 114.07, 116.17, 125.79, 127.53,
Methyl (2R,6S)‑2,6‑bis(4‑methoxyphenyl)‑1‑phe‑
nyl‑4‑(phenylamino)‑1,2,5,6‑tetrahydropyridine‑3‑carbox‑
ylate (8h) White solid; 90% yield; mp 185–187 °C; FT-IR
1 3

Journal of the Iranian Chemical Society
Table 3 Results of the reaction under diferent conditions
Entry
Solvent
Temperature (°C)
Catalyst (g)
Time (h)
Yield (%)a
1
2
3
4
5
6
10
11
12
13
Water
r.t.
r.t.
r.t.
r.t.
r.t.
65
r.t.
r.t.
r.t.
r.t.
Sulfonated AlPO4 (0.05 g)
Sulfonated AlPO4 (0.05 g)
Sulfonated AlPO4 (0.05 g)
Sulfonated AlPO4 (0.05 g)
Sulfonated AlPO4 (0.05 g)
Sulfonated AlPO4 (0.05 g)
Sulfonated AlPO4 (0.1 g)
Sulfonated AlPO4 (0.15 g)
Sulfonated AlPO4 (0.2 g)
–
12
11
10
7
12
5
40
52
60
72
36
65
86
94
92
–
Acetonitrile
Methanol
Ethanol
–
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
5
3.5
3.5
24
All reactions were carried out using 5a (2.0 mmol), 6a (2.0 mmol), and 7a (1.0 mmol) in the presence of the catalyst and solvent under air
atmosphere
aYield of the isolated product
127.77, 128.97, 134.68, 135.92, 138.00, 147.08, 156.43,
158.18, 158.79, 168.64.
3H, CH3), 2.66 (dd, J = 15.0, 2.5 Hz, 1H, H′-5), 2.88 (dd,
J = 15.0, 5.0 Hz, 1H, H″-5), 4.30–4.40 (m, 1H, OCHaHb),
4.44–4.54 (m, 1H, OCHaHb), 5.07–5.09 (m, 1H, H-6), 6.23–
6.30 (m, 2H, ArH), 6.36 (s, 1H, H-2), 6.43–6.50 (m, 2H,
ArH), 6.75–6.85 (m, 4H, ArH), 7.10–7.26 (m, 8H, ArH),
10.24 (s, 1H, NH); 13C NMR (62.9 MHz, CDCl3) δ (ppm):
14.81, 21.03, 21.13, 33.63, 55.41, 58.16, 59.72, 98.30,
113.58, 113.69, 115.06, 115.41, 115.78, 126.35, 126.57
127.90, 128.03, 128.98, 129.38, 133.94, 133.99, 135.93,
136.88, 139.74, 140.70, 143.58, 153.09, 156.03, 156.83,
158.75, 162.65, 168.26.
Methyl (2R,6S)‑2,6‑bis(4‑chlorophenyl)‑1‑(p‑tolyl)‑4‑(p‑tolyl‑
amino)‑1,2,5,6‑tetrahydropyridine‑3‑carboxylate (8i) White
solid; 87% yield; mp 213–215 °C; FT-IR (KBr cm-1): 794, 979,
1010, 1072, 1180, 1257, 1512, 1581, 1650, 2862, 3016, 3255,
3442 cm−1; 1H NMR (250 MHz, CDCl3) δ (ppm): 2.19 (s, 3H,
CH3), 2.30 (s, 3H, CH3), 2.72 (dd, J= 15.0, 2.5 Hz, 1H, H′-5),
2.81 (dd, J= 15.0, 5.0 Hz, 1H, H″-5), 3.93 (s, 3H, OCH3), 5.06–
5.09 (m, 1H, H-6), 6.30 (d, J = 10.0 Hz, 2H, ArH), 6.34 (s,
1H, H-2), 6.38 (d, J = 7.5 Hz, 2H, ArH), 6.90 (d, J = 7.5 Hz,
2H, ArH), 6.97 (d, J = 7.5 Hz, 2H, ArH), 7.08 (d, J = 10.0 Hz,
Methyl (2R, 6S)‑2, 6‑bis(4‑ chlorophenyl)‑1‑phe ‑
nyl‑4‑(phenylamino)‑1,2,5,6‑tetrahydropyridine‑3‑carbox‑
ylate (8k) White solid; 91% yield; mp 226–228 °C; FT-IR
(KBr cm-1): 694, 748, 856, 979, 1072, 1188, 1265, 1326,
1372, 1404, 1504, 1596, 1651, 2869, 3039, 3240 cm−1;
1H NMR (250 MHz, CDCl3) δ (ppm): 2.78 (dd, J = 15.0,
2.5 Hz, 1H, H′-5), 2.88 (dd, J = 15.0, 5.0 Hz, 1H, H″-5),
3.96 (s, 3H, OCH3), 5.13–5.16 (m, 1H, H-6), 6.42–6.52 (m,
5H, H-2 and ArH), 6.68 (t, J = 7.5 Hz, 1H, ArH), 7.08–7.28
(m, 13H, ArH), 10.31 (s, 1H, NH); 13C NMR (62.9 MHz,
CDCl3) δ (ppm): 33.77, 51.27, 54.80, 57.41, 97.61, 113.00,
116.84, 125.78, 126.11, 127.87, 128.15, 128.49, 128.85,
2H, ArH), 7.24–7.28 (m, 6H, ArH), 10.20 (s, 1H, NH); 13
C
NMR (62.9 MHz, CDCl3) δ (ppm): 20.18, 20.96, 33.64, 51.12,
54.86, 57.36, 97.01, 112.96, 125.75, 125.89, 127.87, 128.12,
128.38, 128.77, 129.63, 132.06, 132.79, 134.96, 135.99,
141.23, 142.71, 144.35, 156.38, 168.36.
Ethyl (2R,6S)‑1‑(4‑fluorophenyl)‑4‑((4‑fluorophenyl)
amino)‑2,6‑di‑p‑tolyl‑1,2,5,6‑tetrahydropyridine‑3‑carbox‑
ylate (8j) White solid; 90% yield; mp 183–185 °C; FT-IR
(KBr cm-1): 1H NMR (250 MHz, CDCl3) δ (ppm): 1.50 (t,
J = 7.5 Hz, 3H, OCH2CH3), 2.36 (s, 3H, CH3), 2.38 (s,
1 3

Journal of the Iranian Chemical Society
Table 4 Five-component synthesis of highly functionalized piperidines
Isolated yield
129.11, 129.15, 132.21, 132.93, 137.66, 141.00, 142.45,
146.52, 156.07, 168.34.
characterized by FT-IR (Fourier-transform infrared spectros-
copy), EDX analysis (energy-dispersive X-ray spectroscopy),
and FE-SEM (feld emission scanning electron microscopy).
Since the position of the acidic peaks (–SO3H) is covered by
AlPO4 in FT-IR spectroscopy, the new catalyst was identifed
by EDX and FE-SEM. The EDX analysis of the newly syn-
thesized catalyst showed peaks for O, Al, P, and S elements
that confrms the major constituents of nanosulfonated AlPO4
(Fig. 1a).
Results and discussion
The AlPO4(SO3H) nanosheets morphology was produced
by adding chlorosulfuric acid to commercially available
AlPO4 in CH2Cl2 solvent at room temperature [25]. It was
1 3

Journal of the Iranian Chemical Society
95
para. In all cases, the reaction proceeded to obtain [1,2,4]
triazolo[5,1-b]quinazolin-8(4H)-one derivatives through a
variety of electron-rich and electron-poor aromatic alde-
hydes. We are pleased to disclose that good to excellent
yields (Table 2).
92
92
90
95
85
75
65
55
45
35
89
Considering the literature focusing on the catalytic
activity of Lewis acids [16, 26, 27], we suggested a mech-
anism for this multi-component N-heterocycle synthe-
sis, in this two plausible mechanisms can be proposed.
Generally, these processes (route A and route B) can be
started via Knoevenagel condensation for the formation of
α, β-unsaturated carbonyl intermediate (intermediate I).
Then, upon the loss of water molecule and nucleophilic
attack of nitrogen in the ring gave intermediate II in route
A. In the next step, intermediate IV was probably formed
by intramolecular nucleophilic attack. Finally, the inter-
mediate may undergo dehydration to give desired product.
The second route (as shown in Scheme 1) was started by
attacking NH2 to carbonyl group of intermediate I and loss
of two water molecules, resulting intermediate VI. Finally,
this intermediate produced the desired product (4a) via
intramolecular cyclization.
1
2
3
4
5
Run
Fig. 2 Catalytic activity of the AlPO4(SO3H) nanosheets in 5 cycles
Finally, FE-SEM images indicated sheet-like nanostruc-
tures of the catalyst. The size and thickness of the nanosheets
measured to be 25–35 nm (Fig. 1b, c).
To fnd out the suitable condition for the reaction, a
series of experiments were performed with the standard
reaction of benzaldehyde (1a), dimedone (2), and 1H-1,2,4-
triazol-3-amine (3) to form 6,6-dimethyl-9-phenyl-5,6,7,9-
tetrahydro-[1,2,4]triazolo[5,1-b]quinazolin-8(4H)-one (4a).
The results are depicted in Table 1. A variety of solvents
such as acetonitrile, ethanol, methanol, and water were
tested to fnd out the best solvent for this transformation.
Among various solvents, acetonitrile was found to give
the best result. When the reaction was carried out under
solvent-free conditions (Table 1, entry 8), the product was
obtained 5%, probably due to the absence of strong interac-
tions between the various reactants. To show the efciency
of the nano-AlPO4(SO3H) in comparison with other cata-
lysts, AlPO4, amino-functionalized AlPO4, CuFe2O4, and
p-dodecylbenzenesulfonic acid were also applied and these
results showed that nano-AlPO4(SO3H) catalyst is better in
viewpoint of reactivity and experimental conditions for this
reaction (Table 1, entries 1–4). After this, we studied the
efect of various amounts of nano-AlPO4(SO3H) catalyst
for the synthesis of 4a. In order to evaluate the appropriate
catalyst loading, a model reaction was carried out using
0.3, 0.2, 0.1 and 0. 05 g of nano-AlPO4(SO3H) in CH3CN
(Table 1, entries 5, 10–12). We also screened the efect of
diferent temperature in the model reaction (Table 1, entries
11, 13–14). The lower amounts of catalyst gave a low yield,
and a larger loading amount of the catalyst (0.3 g) neither
increases the yield nor shortens the conversion time. So,
0.1 g of catalyst in CH3CN at 50 °C was found to be the
optimal quantity and sufcient to push the reaction forward
(Table 1, entry 13).
Motivated from the efcient catalytic activity of nano-
AlPO4(SO3H) for the synthesis of quinazolinones, we
explored its catalytic activity for the synthesis of highly
functionalized piperidines via one-pot, fve-component reac-
tion of aromatic aldehydes, aromatic amines, and methyl or
ethyl acetoacetate in EtOH at room temperature.
In the frst step, we optimized the conditions for the fve-
component reaction using aniline (2.0 mmol), 4-methyl ben-
zaldehyde (2.0 mmol), and methyl acetoacetate (1.0 mmol)
as model reaction in various solvents, temperatures, and
in the presence of various amounts of catalyst loading
(Table 3). As evident from Table 3, the best result was
observed in ethanol at room temperature in the presence of
0.15 g of the catalyst (Table 3, entry 11).
To establish the generality and applicability of this
method in fve-component synthesis of piperidine deriva-
tives, a variety of substituted aromatic aldehydes and amines
(containing electron-withdrawing or electron-donating
groups) were subjected to the same reaction conditions
to furnish the corresponding piperidine derivatives. In all
cases, the reaction proceeded to obtain piperidines in good
yields (Table 4).
The reusability of the catalyst is an important factor from
an economical and environmental point of views and has
attracted much attention in recent years. Thus, the reusabil-
ity of nano-AlPO4(SO3H) was examined in the synthesis of
4a. After each run, the catalyst was centrifugation, washed
with dichloromethane, dried under atmosphere, and utilized
directly in the next cycle. As shown in Fig. 2, the yield and
time of the model reaction for fve runs were almost the
same as the frst run (Fig. 2).
After optimization of the reaction conditions, the cata-
lytic activity of nano-AlPO4(SO3H) was tested by diferent
aromatic aldehydes bearing Me, Cl, isopropyl, OMe, NO2,
F, dimethyl amine, and Br substitutes at ortho, meta, and
1 3

Journal of the Iranian Chemical Society
7. H. Sharghi, M. Aberi, Synlett 25, 1111–1115 (2014)
Conclusion
8. N.G. Singh, R. Nagarajaprakash, J.W.S. Rani, C. Kathing, R. Non-
gruma, R. Nongkhlaw, New J. Chem. 39, 3908–3915 (2015)
9. R.G. Puligoundla, S. Karnakanti, R. Bantu, K. Nagaiah, S.B. Kon-
dra, L. Nagarapu, Tetrahedron Lett. 54, 2480–2483 (2013)
10. N. Kaur, K. Kaur, T. Raj, G. Kaur, A. Singh, T. Aree, S.J. Park, T.J.
Kim, N. Singh, D.O. Jang, Tetrahedron 71, 332–337 (2015)
11. P. Kar, B. Mishra, S. Pradhan, J. Mol. Catal. A: Chem. 387, 103–111
(2014)
In summary, new AlPO4(SO3H) nanosheets were prepared
and the heterogeneous nanocatalysts were characterized by
FE-SEM, EDX, and FT-IR analysis. The nanocatalyst was
used for the synthesis of a series of [1,2,4]triazolo quina-
zolinone and piperidine derivatives. The conditions are
mild, and a wide range of functional groups can be toler-
ated. Using AlPO4(SO3H) nanosheets as heterogeneous
catalyst ofers some advantages including easy work-up,
short reaction time, good to excellent yields, and no need to
purify with column chromatography. Moreover, the catalyst
could be successfully recovered and recycled by a simple
centrifugation for at least fve times without a noticeable
their catalytic activity.
12. V. Palermo, A. Sathicq, N. Liberto, S. Fernandes, P. Langer, J. Jios,
G. Romanelli, Tetrahedron Lett. 57, 2049–2054 (2016)
13. M.M. Khan, S. Khan, S. Iqbal, R.Yousuf Saigal, New J. Chem. 40,
7504–7512 (2016)
14. S. Verma, S.L. Jain, B. Sain, Beilstein J. Org. Chem. 7, 1334–1341
(2011)
15. M.R. Mousavi, M.T. Maghsoodlou, Monatsh. Chem. 145, 1967–
1973 (2014)
16. R. Ramesh, S. Maheswari, M. Arivazhagan, J.G. Malecki, A. Lali-
tha, Tetrahedron Lett. 58, 3905–3909 (2017)
17. H. Sharghi, M. Aberi, M.M. Doroodmand, P. Shiri, J. Iran. Chem.
Soc. 14, 1557–1573 (2017)
Acknowledgements We gratefully acknowledge the fnancial support
of this work by the Shiraz University Research Council.
18. M.R. Mousavi, J. Aboonajmi, M.T. Maghsoodlou, N. Hazeri, J.
Chem. Res. 38, 76–79 (2014)
19. N. Hazeri, M.T. Maghsoodlou, S.M. Habibi-Khorassani, J. Aboona-
jmi, S.S. Sajadikhah, J. Chin. Chem. Soc. 60, 355–358 (2013)
20. H. Sharghi, P. Shiri, M. Aberi, Mol. Divers. 18, 559–575 (2014)
21. H. Sharghi, M. Aberi, M.M. Doroodmand, Mol. Divers. 19, 77–85
(2015)
References
1. F.M. Bautista, V. Caballero, J.M. Campelo, D. Luna, J.M. Mari-
nas, A.A. Romero, I. Romero, I. Serrano, A. Llobet, Top. Catal.
40, 193–205 (2006)
22. H. Sharghi, J. Aboonajmi, M. Mozafari, M.M. Doroodmand, M.
Aberi, Appl. Organomet. Chem. (in press)
2. B.H. Rotstein, S. Zaretsky, V. Rai, A.K. Yudin, Chem. Rev. 114,
8323–8359 (2014)
23. H. Sharghi, P. Shiri, Synthesis 47, 1131–1146 (2015)
24. H. Sharghi, P. Shiri, M. Aberi, Synthesis 46, 2489–2498 (2014)
25. M.A. Zolfgol, R. Ayazi-Nasrabadi, S. Baghery, RSC Adv. 5, 71942–
71954 (2015)
3. H. Bienaymé, C. Hulme, G. Oddon, P. Schmitt, Chem. Eur. J. 6,
3321–3329 (2000)
4. J.E. Biggs-Houck, A. Younai, J.T. Shaw, Curr. Opin. Chem. Biol.
14, 371–382 (2010)
26. M.R. Mousavi, M.T. Maghsoodlou, N. Hazeri, S.M. Habibi-Kho-
rassani, J. Iran. Chem. Soc. 12, 1419–1424 (2015)
27. K. Kulangiappar, M. Anbukulandainathan, T. Raju, Synth. Com-
mun. 1, 2494–2505 (2014)
5. S. Brauch, S.S. van Berkel, B. Westermann, Chem. Soc. Rev. 42,
4948–4962 (2013)
6. A. Khalaf-Nezhad, M. Shekouhy, H. Sharghi, J. Aboonajmi, A.
Zare, RSC Adv. 6, 67281–67289 (2016)
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