FSM-16/AEPC-SO3H: Synthesis, Characterization and Its Application for the Catalytic Preparation of 1,8-Dioxo-octahydroxanthene and Tetrahydrobenzo[b]pyran Derivatives

Article abstract of DOI:10.1007/s10562-018-2623-x

A new acidic mesoporous catalyst (FSM-16/AEPC-SO₃H) was successfully synthesized and characterized by FT-IR, TGA, XRD, SEM, TEM, EDS and BET techniques. The FSM-16/AEPC-SO₃H showed excellent catalytic activity for the synthesis of 1,

Full text of DOI:10.1007/s10562-018-2623-x

Catalysis Letters
https://doi.org/10.1007/s10562-018-2623-x
FSM-16/AEPC-SO3H: Synthesis, Characterization and Its Application
for the Catalytic Preparation of 1,8-Dioxo-octahydroxanthene
and Tetrahydrobenzo[b]pyran Derivatives
Maryam Hajjami1 · Fatemeh Gholamian1 · Robert H. E. Hudson2 · Ali Mohammad Sanati3
Received: 13 June 2018 / Accepted: 20 November 2018
© Springer Science+Business Media, LLC, part of Springer Nature 2018
Abstract
A new acidic mesoporous catalyst (FSM-16/AEPC-SO3H) was successfully synthesized and characterized by FT-IR, TGA,
XRD, SEM, TEM, EDS and BET techniques. The FSM-16/AEPC-SO3H showed excellent catalytic activity for the synthesis
of 1,8-dioxo-octahydroxanthene and tetrahydrobenzo[b]pyran derivatives. The synthesized catalyst can also be recycled.
Graphical Abstract
Keywords Mesoporous catalyst · FSM-16/AEPC-SO3H · 1,8-Dioxo-octahydroxanthene · Tetrahydrobenzo[b]pyran
1 Introduction
FSM-16 is one of the mesoporous materials whose pore size
in the range 2–50 nm in structure [1] and has attracted atten-
tion in the field of adsorption, catalytic chemistry [2], sepa-
ration membrane, fixing agent for biomolecule and semicon-
ductor cluster, functional electronics and photonics materials
[1]. FSM-16 is structurally similar to the MCM-41 solid;
both of them have uniform mesoporous channel structure [3]
with a hexagonal array [1]. Despite the mentioned similari-
ties, FSM-16 and MCM-41, have the differences such that
FSM-16 has higher structural stability than MCM-41 [4].
Therefore, development of synthetic procedures that produce
Electronic supplementary material The online version of this
article (https://doi.org/10.1007/s10562-018-2623-x) contains
supplementary material, which is available to authorized users.
* Maryam Hajjami
mhajjami@yahoo.com; m.hajjami@ilam.ac.ir
1
Department of Chemistry, Faculty of Science, Ilam
University, P.O. Box 69315516, Ilam, Iran
2
Department of Chemistry, The University of Western
Ontario, London, ON N6A 5B7, Canada
3
Department of Environmental Science, Persian Gulf
Research Institute, Persian Gulf University, Bushehr, Iran
Vol.:(0123456789)
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M. Hajjami et al.
new heterogeneous catalysts based on FSM-16 is an ever-
challenging objective.
were measured by FT-IR, Bruker, Germany spectroscopy.
The thermogravimetric analysis of catalyst was determined
by TGA, PerkinElmer Pyris Diamond, U.K. The analysis of
XRD pattern used for the synthesized catalyst was recog-
nized by XRD, X’Pert PRO MPD, PANalytical, Netherland.
The energy dispersive X-ray was measured with instruments
EDX, TESCAN MIRA, Czech. Also the instruments of
Brunauer–Emmett–Teller and scanning electron micros-
copy have this character respectively: BET, Micromeritics,
Asap2020, USA and SEM, FESEM-TESCAN MIRA3. The
analysis of transmission electron microscopy (TEM), was
done using a Philips 420 transmission microscopy, with an
accelerating voltage of 60.0 kV.
Itaconic acid was discovered by Baup in 1837 and is a
five carbon chemical building block, fully sustainable, non-
toxic and inexpensive [5]. Uses for this compound include
plastic, rubber, detergents, textile industries, production of
biodegradable green plastics and in the synthesis of different
heterocycles [6].
1,8-Dioxo-octahydroxanthenes are an important family of
heterocycle compound containing phenyl substituted pyran
ring which is attached on either side with two cyclohex-
anone rings [7]. Due to their numerous applications in leuco
dyes, in laser technology, as pH-sensitive fluorescent materi-
als for the visualization of biomolecular assemblies [8], in
photodynamic therapy [9], in chiroptical molecular switches
[10], also their many pharmacological properties such as
antinociceptive activities [11], antibacteria, antiviral, anti-
inflammatory, anti-depressants and antimalarial agents [9]
have attracted much attention on their synthesis with the
use of various catalysts. Basically, in order to synthesis the
xanthenedione derivatives [7, 12–15] and benzoxanthene
derivatives [16–19] in the presence of various catalysts have
been reported.
2.2 Synthesis of FSM‑16/AEPC‑SO3H
The FSM-16 was prepared by the method that was presented
in literature [25]. The itaconic acid (1 mmol) with ethylen-
ediamine (1 mmol) was reacted in H2O under reflux condi-
tion for 24 h [26]. Then the solvent was evaporated to afford
N-(2-aminoethyl)-2-pyrrolidone-4-carboxylic acid (AEPC)
and recrystallized in EtOH. FSM-16 (1 g) was sonicated in
deionized water for 20 min. Then AEPC (2 g) was added to
reaction mixture under N2 atmosphere at 80 °C for 21 h. The
reaction mixture was filtered, washed with H2O and dried
in room temperature for overnight. Chlorosulfuric acid was
applied for acidification of catalyst [27]. The 0.5 g of synthe-
sized solid (FSM-16/AEPC) was sonicated in n-hexane for
20 min and then, chlorosulfuric acid (1.5 ml) was added drop
of drop and stirred for 3 h in ice bath. Finally, the synthe-
sized catalyst was washed with n-hexane, EtOH then CH2Cl2
and dried in room temperature.
Another group of heterocycle compounds contain-
ing oxygen are tetrahydrobenzo[b]pyran derivatives.
Tetrahydrobenzo[b]pyran has attracted considerable atten-
tion not only for the biological properties such as pasmo-
lytic, diuretic, anticoagulant, anticancer, antianaphylactic,
antioxidant, antileishmanial, antibacterial, antifungal, hypo-
tensive, antiviral, antiallergenic, and antitumor activities
[20] but also for the treatment of neurodegenerative disease,
for example, AIDS associated dementia, Parkinson’s disease,
Alzheimer’s disease, Huntington’s disease, amyotrophic lat-
eral sclerosis and Down syndrome. Additionally, these com-
pounds widely used as potential biodegradable agrochemi-
cals, cosmetics, photoactive materials and pigments [21].
Thus, in a view of their wide applicability the devel-
opment highly efficient procedures for the synthesis of
tetrahydrobenzo[b]pyran have attracted a great deal of
attention [20]. The conventional synthesis involves a three
component condensation of malononitrile, an aldehyde and
dimedone in different conditions [21–23]. Also synthesis of
benzopyran derivatives by condensation reaction of substi-
tuted salicyaldehydes and substituted 1,3-hexanediones in
the presence of catalyst have been reported [24].
2.3 General Procedure for the Synthesis
of 1,8‑Dioxo‑octahydroxanthene Derivatives
A test tube including aldehyde (1 mol) and dimedone (2 mol)
in the presence of FSM-16/AEPC-SO3H (0.45 mol%) as
catalyst was heated at 120 °C. After the completion of reac-
tion (monitored by TLC), the hot EtOH was added to reac-
tion mixture and the catalyst was separated by filtration. The
products were recrystallization with EtOH.
2.4 General Procedure for the Synthesis
of Tetrahydrobenzo[b]pyran Derivatives
Aldehyde (1 mol), dimedone (1 mol), malononitrile (1 mol)
and FSM-16/AEPC-SO3H (0.6 mol%) as catalyst were
mixed in H2O: EtOH (3:1 ml) at 80 °C. Upon completion
of the reaction checked by TLC, the reaction mixture was
cooled at room temperature, filtered and washed by H2O.
Then hot EtOH was poured on precipitate until the product
2 Experimental
2.1 Materials and Physical Measurements
The chemicals used for this work, were purchased from
Merck and Aldrich chemical companies. The FT-IR spectra
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FSM-16/AEPC-SO3H: Synthesis, Characterization and Its Application for the Catalytic…
is solved. Finally, products were recrystallized for more
purification.
3.85(s,3H) 4.69 (s, 1H), 6.69–6.77 (m, 2H), 6.89 (s, 1H)
ppm. 13C NMR (CDCl3, 75 MHz): δ=27.3, 29.3, 31.2, 32.2,
40.9, 50.7, 55.7, 110.8, 112.2, 115.7, 120.1, 137, 147.4,
148.4, 162.1, 196.5 ppm. IR (KBr): 3072, 3025, 2932, 2877,
1669, 1622, 1513, 1459, 1360, 1262, 1196, 1140, 1024,
933 cm−1.
2.5 Characterization Data of All Compounds
2.5.1 3,3,6,6-Tetramethyl-9-(4-chloro-phenyl)-1,8-dioxo
octahydroxanthene
2.5.6 3,3,6,6-Tetramethyl-9-(3-nitro-phenyl)-1,8-dioxo
octahydroxanthene
1H NMR (300 MHz, CDCl3): δ=0.99 (s, 6H), 1.1 (s, 6H),
2.13–2.27 (q, J=16.2 Hz, 4H), 2.46 (s, 4H), 4.71 (s, 1H),
7.17–7.26 (m, 4H) ppm. 13C NMR (CDCl3, 75 MHz):
δ=27.3, 29.3, 31.4, 32.2, 40.8, 50.7, 115.3, 128.2, 129.8,
132, 142.7, 162.4, 196.4 ppm. IR (KBr): 3026, 2927, 2876,
1662, 1470, 1363, 1198, 1151, 1007, 846 cm−1.
1H NMR (400 MHz, CDCl3): δ=1.02 (s, 6H), 1.1 (s, 6H),
2.15–2.28 (q, J = 16 Hz, 4H), 2.5 (s, 4H), 4.85 (s, 1H),
7.28–7.43 (m, 1H), 7.80–7.82 (m, 1H), 7.98–8.04 (m, 2H)
ppm. 13C NMR (CDCl3, 100 MHz): δ = 27.3, 29.3, 32.1,
32.2, 40.8, 50.6, 114.5, 121.6, 128.8, 135.6, 146.3, 148.3,
163, 196.4 ppm. IR (KBr): 2958, 2934, 1657, 1624, 1524,
1472, 1396, 1357, 1201, 1166, 816 cm−1.
2.5.2 3,3,6,6-Tetramethyl-9-(4-bromo-phenyl)-1,8-dioxo
octahydroxanthene
1H NMR (400 MHz, CDCl3): δ=1.00 (s, 6H), 1.1 (s, 6H),
2.16–2.28 (q, J = 16 Hz, 4H), 2.48 (s, 4H), 4.72 (s, 1H),
7.18–7.20 (d, J = 8 Hz, 2H), 7.35–7.37 (d, J = 8 Hz, 2H)
ppm. 13C NMR (CDCl3, 100 MHz): δ = 27.3, 29.3, 31.5,
32.2, 40.8, 50.7, 115.2, 120.2, 130.2, 131.1, 143.2, 162.4,
196.3 ppm. IR (KBr): 3026, 2955, 2873, 1666, 1628, 1487,
1467, 1362, 1198, 1165, 1005, 846 cm−1.
2.5.7 3,3,6,6-Tetramethyl-9-(3-hydroxy-phenyl)-1,8-dioxo
octahydroxanthene
1H NMR (300 MHz, CDCl3): δ=0.99 (s, 6H), 1.09 (s, 6H),
2.16–2.28 (q, J=16.5 Hz, 4H), 2.45 (s, 4H), 4.76 (s, 1H),
6.54–6.58 (m, 1H), 6.68–6.70 (d, J=9 Hz, 1H), 7.0-7.03 (m,
2H), 7.06–7.08 (m, 1H) ppm. 13C NMR (CDCl3, 75 MHz):
δ=27.4, 29.2, 31.7, 32.2, 40.8, 50.6, 113.6, 115.6, 116.4,
119.5, 129.12, 145.5, 156, 162.6, 197 ppm. IR (KBr): 3382,
3035, 2959, 2927, 1661, 1605, 1458, 1363, 1255, 1199,
977 cm−1.
2.5.3 3,3,6,6-Tetramethyl-9-(4-fluoro-phenyl)-1,8-dioxo
octahydroxanthene
1H NMR (400 MHz, CDCl3): δ=1.02 (s, 6H), 1.1 (s, 6H),
2.17–2.26 (q, J = 16 Hz, 4H), 2.48 (s, 4H), 4.75 (s, 1H),
6.89–7.29 (m, 4H) ppm.13C NMR (CDCl3, 100 MHz):
δ=27.3, 29.3, 31.2, 32.2, 40.8, 50.7, 114.7, 115.5, 129.8,
160, 162.3, 162.6, 196.4 ppm. IR (KBr): 2958, 2927, 2873,
2819, 1661, 1629, 1508, 1398, 1364, 1223, 1198, 1141,
1002, 851 cm−1.
2.5.8 3,3,6,6-Tetramethyl-9-(4-hydroxy-phenyl)-1,8-dioxo
octahydroxanthene
1H NMR (400 MHz, CDCl3): δ=1.02 (s, 6H), 1.11 (s, 6H),
2.18–2.28 (q, J = 16 Hz, 4H), 2.48 (s, 4H), 4.69 (s, 1H),
6.56–6.58 (d, J=8 Hz, 2H), 7.08–7.10 (d, J=8 Hz, 2H), 7.28
(s,1H) ppm. 13C NMR (CDCl3, 100 MHz): δ=27.4, 29.2,
30, 32.3, 40.9, 50.8, 115.2, 115.8, 129.3, 135.7, 154.6, 162,
197 ppm. IR (KBr): 3405, 2962, 2930, 1662, 1616, 1513,
1361, 1247, 1165, 1003, 838 cm−1.
2.5.4 3,3,6,6-Tetramethyl-9-(4-methoxy-phenyl)-1,8-dioxo
octahydroxanthene
1H NMR (400 MHz, CDCl3): δ=1.01 (s, 6H), 1.1 (s, 6H),
2.16–2.27 (q, J=16 Hz, 4H), 2.47 (s, 4H), 3.75 (s, 3H), 4.71
(s, 1H), 6.76–6.78 (d, J=8 Hz, 2H), 7.21–7.23 (d, J=8 Hz,
2H) ppm.13C NMR (CDCl3, 100 MHz): δ=27.3, 29.3, 30,
32, 40.9, 50.8, 55.1, 113.4, 115.8, 129.3, 136.5, 157.9,
162.1, 196.5 ppm. IR (KBr): 3059, 2961, 2882, 2875, 1664,
1628, 1511, 1462, 1357, 1260, 1194, 1137, 1032, 931 cm−1.
2.5.9 3,3,6,6-Tetramethyl-9-(2,4-dichloro-phenyl)-1,8-di-
oxo octahydroxanthene
1H NMR (400 MHz, CDCl3): δ=1.04 (s, 6H), 1.1 (s, 6H),
2.16–2.27 (q, J = 16 Hz, 4H), 2.47 (s, 4H), 4.97 (s, 1H),
7.15–7.45 (m, 3H) ppm. 13C NMR (CDCl3, 100 MHz):
δ = 27.4, 29.3, 32, 40.8, 50.7, 113.3, 126.7, 129.8, 132.8,
134, 138.6, 163.2, 196.5 ppm. IR (KBr): 3072, 3026, 2981,
2876, 1661, 1624, 1586, 1471, 1389, 1360, 1199, 1102,
860 cm−1.
2.5.5 3,3,6,6-Tetramethyl-9-(3,4-dimethoxy-phenyl)-1,8-di-
oxo octahydroxanthene
1H NMR (300 MHz, CDCl3): δ=0.99 (s, 6H), 1.09 (s, 6H),
2.14–2.26 (q, J=16.5 Hz, 4H), 2.45 (s, 4H), 3.79 (s, 3H),
1 3

M. Hajjami et al.
2.5.10 3,3,6,6-Tetramethyl-9-(2-nitro-phenyl)-1,8-dioxo
octahydroxanthene
(m, 4H) ppm. 13C NMR (DMSO, 100 MHz): δ=27.3, 28.8,
32.3, 35.4, 50.4, 58.5, 113, 115.4, 115.6, 120, 129.5, 141,
158, 160, 162, 196.1 ppm. IR (KBr): 3358, 3180, 2959,
2894, 2190, 1676, 1637, 1604, 1506, 1466, 1368, 1216,
1161, 1033, 858, 776 cm−1.
1H NMR (400 MHz, CDCl3): δ=1.03 (s, 6H), 1.12 (s, 6H),
2.14–2.27 (q, J = 16 Hz, 4H), 2.49 (s, 4H), 5.53 (s, 1H),
7.24–7.47 (m, 3H), 7.76–7.78(d, J = 8 Hz, 1H) ppm. 13C
NMR (CDCl3, 100 MHz): δ=27.6, 28.9, 29.4, 29.6, 29.7,
32, 40.9, 50.6, 114, 124.6, 127.2, 131.9, 137.8, 149.9, 162,
196 ppm. IR (KBr): 2959, 2844, 1665, 1626, 1528, 1384,
1354, 1205, 1150, 797 cm−1.
2.5.15 2-Amino-3-cyano-7,7-dimethyl-4-(4-nitrophenyl)-5-
oxo-4H-5,6,7,8-tetrahydro benzopyran
1H NMR (400 MHz, DMSO-d6): δ=0.97 (s, 3H), 1.06 (s,
3H), 2.10–2.14 (d, J=16 Hz, 1H), 2.25–2.29 (d, J=16 Hz,
1H), 2.50–2.59 (m, 2H), 4.35 (s, 1H), 7.18 (s, 2H), 7.44–7.46
(d, J=8 Hz, 2H), 8.17–8.19 (d, J=8 Hz, 2H) ppm. 13C NMR
(DMSO, 100 MHz): δ=27.4, 28.7, 32.3, 36.1, 50.3, 56.5,
57.4, 112.2, 119.8, 124.1, 129.1, 146.7, 152.7, 159, 163.5,
196 ppm. IR (KBr): 3506, 3385, 3135, 2966, 2934, 2189,
1683, 1657, 1663, 1518, 1369, 1344, 1254, 1216, 1143,
1041, 828, 564 cm−1.
2.5.11 3,3,6,6-Tetramethyl-9-(4-nitro-phenyl)-1,8-dioxo
octahydroxanthene
1H NMR (400 MHz, CDCl3): δ=1.01 (s, 6H), 1.14 (s, 6H),
2.17–2.30 (q, J = 16 Hz, 4H), 2.52 (s, 4H), 4.85 (s, 1H),
7.48–7.50 (d, J = 8 Hz, 2H), 8.10–8.12 (d, J = 8 Hz, 2H)
ppm. 13C NMR (CDCl3, 100 MHz): δ = 27.3, 29.3, 32.2,
32.3, 40.8, 50.6, 114.5, 123.4, 129.3, 146.5, 151.5, 162.1,
196.2 ppm. IR (KBr): 2924, 2854, 1659, 1515, 1467, 1398,
1201, 1165, 1001, 865 cm−1.
2.5.16 2-Amino-3-cyano-7,7-dimethyl-4-(3-nitrophenyl)-5-
oxo-4H-5,6,7,8-tetrahydro benzopyran
2.5.12 2-Amino-3-cyano-7,7-dimethyl-4-(4-chlorophenyl)-
5-oxo-4H-5,6,7,8-tetrahydro benzopyran
1H NMR (400 MHz, DMSO-d6): δ=0.96 (s, 3H), 1.05 (s,
3H), 2.10–2.14 (d, J=16 Hz, 1H), 2.26–2.30(d, J=16 Hz,
1H), 2.51–2.60 (m, 2H), 4.43 (s, 1H), 7.19 (s, 2H), 7.61–7.69
(m, 2H), 7.99–8.1 (m, 2H) ppm. 13C NMR (DMSO,
100 MHz): δ = 27.2, 28.8, 32.3, 35.8, 50.3, 57.6, 112.2,
119.8, 122.1, 122.2, 130.5, 134.6, 147.5, 148.2, 159.1,
163.6, 196.2 ppm. IR (KBr): 3432, 3327, 2958, 2875, 2204,
1681, 1662, 1600, 1531, 1372, 1349, 1210, 1093, 1038, 902,
822 cm−1.
1H NMR (400 MHz, DMSO-d6): δ=0.95 (s, 3H), 1.04 (s,
3H), 2.09–2.13 (d, J=16 Hz, 1H), 2.24–2.28 (d, J=16 Hz,
1H), 2.47–2.56 (m, 2H), 4.21 (s, 1H), 7.07 (s, 2H), 7.17–7.19
(d, J=8 Hz, 2H), 7.34–7.36 (d, J=8 Hz, 2H) ppm. 13C NMR
(DMSO, 100 MHz): δ=27.3, 28.8, 31.1, 32.3, 35.6, 50.4,
58.2, 112.8, 120, 128.7, 129.6, 131.6, 144.2, 158.7, 163,
196.1 ppm. IR (KBr): 3382, 3323, 3264, 2189, 1677, 1638,
1491, 1407, 1217, 1162, 884 cm−1.
2.5.17 2-Amino-3-cyano-7,7-dimethyl-4-(2-nitrophenyl)-5-
oxo-4H-5,6,7,8-tetrahydro benzopyran
2.5.13 2-Amino-3-cyano-7,7-dimethyl-4-(4-bromophenyl)-
5-oxo-4H-5,6,7,8-tetrahydro benzopyran
1H NMR (400 MHz, DMSO-d6): δ= 0.9 (s, 3H), 1.02 (s,
3H), 2.00-2.04 (d, J=16 Hz, 1H), 2.19–2.23 (d, J=16 Hz,
1H), 2.48–2.57 (m, 2H), 4.94 (s, 1H), 7.20 (s, 2H), 7.35–7.37
(d, J=8 Hz, 1H), 7.41–7.45 (t, J=8 Hz, 1H), 7.67–7.69 (m,
1H), 7.81–7.83(d, J= 8 Hz, 1H) ppm. 13C NMR (DMSO,
100 MHz): δ=27.2, 28.8, 30.4, 32.3, 50, 56.8, 112.8, 119.5,
124.2, 128.3, 130.7, 139.4, 149.4, 159, 163, 196 ppm. IR
(KBr): 3471, 3335, 2961, 2895, 2194, 1689, 1663, 1598,
1525, 1409, 1360, 1254, 1215, 1043, 862 cm−1.
1H NMR (400 MHz, DMSO-d6): δ=0.95 (s, 3H), 1.06 (s,
3H), 2.09–2.13 (d, J=16 Hz, 1H), 2.23–2.27 (d, J=16 Hz,
1H), 2.74–2.56 (m, 2H), 4.19 (s, 1H), 7.07 (s, 2H), 7.11–7.13
(d, J=8 Hz, 2H), 7.48–7.50 (d, J=8 Hz, 2H) ppm. 13C NMR
(DMSO, 100 MHz): δ = 19, 27.3, 28.8, 32.3, 35.6, 50.4,
56.5, 58.1, 112.7, 120, 121, 129.9, 131.7, 144.6, 158.7, 160,
196.1 ppm. IR (KBr): 3361, 3317, 3255, 3193, 2960, 2852,
2189, 1685, 1650, 1478, 1404, 1379, 1252, 1142, 1083, 840,
564 cm−1.
2.5.18 2-Amino-3-cyano-7,7-dimethyl-4-(4-methoxypheny
l)-5-oxo-4H-5,6,7,8-tetrahydro benzopyran
2.5.14 2-Amino-3-cyano-7,7-dimethyl-4-(4-fluorophenyll)-
5-oxo-4H-5,6,7,8-tetrahydro benzopyran
1H NMR (300 MHz, DMSO-d6): δ=0.93 (s, 3H), 1.02 (s,
3H), 2.04–2.10 (d, J=18 Hz, 1H), 2.20–2.26(d, J=18 Hz,
1H), 2.47–2.49 (m, 2H), 3.69 (s, 3H), 4.01 (s, 1H), 6.81–6.84
(d, J=9 Hz, 2H), 6.95 (s, 2H), 7.02–7.05 (d, J=9 Hz, 2H)
ppm. 13C NMR (DMSO, 100 MHz): δ = 26.8, 28.5, 31.8,
1H NMR (400 MHz, DMSO-d6): δ=0.95 (s, 3H), 1.04 (s,
3H), 2.09–2.13 (d, J=16 Hz, 1H), 2.23–2.27 (d, J=16 Hz,
1H), 2.50–2.52 (m, 2H), 4.21 (s, 1H), 7.03 (s,2H), 7.09–7.19
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FSM-16/AEPC-SO3H: Synthesis, Characterization and Its Application for the Catalytic…
34.8, 50, 55, 58.6, 113, 113.7, 119.9, 128.3, 136.9, 157.9,
158.4, 162.2, 195.7 ppm. IR (KBr): 3361, 3186, 2960, 2192,
1652, 1606, 1507, 1463, 1252, 1030 cm−1.
119.6, 120.3, 137.8, 148, 148.9, 158.8, 162.7, 196.1 ppm.
IR (KBr): 3395, 3330, 3258, 3215, 2934, 2194, 1680, 1658,
1512, 1465, 1367, 1214, 1141, 1033, 749 cm−1.
2.5.19 2-Amino-3-cyano-7,7-dimethyl-4-(3,4-dimethoxyph
enyl)-5-oxo-4H-5,6,7,8-tetrahydro benzopyran
2.5.20 2-Amino-3-cyano-7,7-dimethyl-4-(4-methylphenyl)-
5-oxo-4H-5,6,7,8-tetrahydro benzopyran
1H NMR (400 MHz, DMSO-d6): δ=0.98 (s, 3H), 1.05 (s,
3H), 2.10–2.14 (d, J=16 Hz, 1H), 2.25–2.29 (d, J=16 Hz,
1H), 2.50–2.53 (m, 2H), 3.71 (s, 3H), 3.72 (s, 3H), 4.14 (s,
1H), 6.65–6.70 (m, 2H), 6.86–6.88 (d, J=8 Hz, 1H), 6.95
(s, 2H) ppm. 13C NMR (DMSO, 100 MHz): δ= 19, 27.1,
28.9, 32.2, 35.5, 50.5, 55.9, 56, 59, 111.5, 112.3, 113.3,
1H NMR (400 MHz, DMSO-d6): δ=0.95 (s, 3H), 1.04 (s,
3H), 2.08–2.12 (d, J=16 Hz, 1H), 2.23–2.27 (d, J=16 Hz,
1H), 2.45–2.56 (m, 2H), 3.72 (s, 3H), 4.13 (s, 1H), 6.84–6.86
(d, J=8 Hz, 2H), 6.96 (s, 2H), 7.05–7.07 (d, J=8 Hz, 2H)
ppm. 13C NMR (DMSO, 100 MHz): δ = 27.2, 28.9, 32.3,
35.2, 50.5, 55.5, 59, 113, 114.1, 120.3, 128.7, 137.3, 158.4,
O
O
NH2
OH
N
NH2
H2O
HO
+
OH
OH
H2N
Reflux,24h
HO
AEPC
O
O
O
O
OH
OH
HO
HO
HO
HO
N
OH
OH
OH
OH
OH
OH
O
HO
HO
H2N
H2N
O
O
HO
HO
HO
OH
OH
OH
N
N
NH2
AEPC
H2O
O
O
O
O
OH
OH
OH
80
OH
°C, N2
OH
21h
FSM-16
FSM-16/AEPC
O
O
N
HO
HO
HO
OH
OH
O
HO3SHN
OH
HO3SHN
O
N
N
NHSO3H
O
O
O
O
O
OH
OH
OH
FSM-16/AEPC-SO3H
Scheme 1 Synthesis of FSM-16/AEPC-SO3H
1 3

M. Hajjami et al.
158.9, 162.6, 196.1 ppm. IR (KBr): 3434, 3382, 3188, 2925,
2193, 1684, 1654, 1509, 1403, 1370, 1254, 1214, 1140,
1035, 569 cm−1.
110
100
90
2.5.21 2-Amino-3-cyano-7,7-dimethyl-4-(2,4-dichlorophen
yl)-5-oxo-4H-5,6,7,8-tetrahydro benzopyran
80
70
1H NMR (300 MHz, DMSO-d6): δ=0.94 (s, 3H), 1.00 (s,
3H), 2.01–2.07 (d, J=18 Hz, 1H), 2.18–2.24 (d, J=18 Hz,
1H), 2.47–2.49 (m, 2H), 4.64 (s, 1H), 7.09 (s, 2H), 7.16–7.19
(d, J=9 Hz, 1H), 7.31–7.34 (dd, J=9 Hz, 1H), 7.49–7.50 (d,
J=3 Hz, 1H) ppm. 13C NMR (DMSO, 75 MHz): δ=26.9,
28.3, 31.8, 32.6, 49.9, 56.2, 111.3, 119.1, 127.7, 128.7,
131.4, 131.8, 133, 140.7, 158.7, 163.3, 195.6. IR (KBr):
3405, 3331, 3258, 3214, 2931, 2868, 2193, 1685, 1652,
1469, 1419, 1366, 1252, 1213, 1039, 856, 795 cm−1.
FSM-16
Catalyst
60
50
40
30
0
100 200 300 400 500 600 700 800 900
Temperature (ₒC)
Fig. 2 TGA profile of FSM-16 and FSM-16/AEPC-SO3H
Fig. 1 The FT-IR spectrum of
FSM-16 (a), FSM-16/AEPC
(b), FSM-16/AEPC-SO3H (c)
1 3

FSM-16/AEPC-SO3H: Synthesis, Characterization and Its Application for the Catalytic…
2.5.22 2-Amino-3-cyano-7,7-dime-
thyl-4(phenyl)-5-oxo-4H-5,6,7,8-tetrahydro benzo-
pyran
1H), 2.48–2.51 (m, 2H), 4.07 (s, 1H), 6.65–6.94 (m, 6H),
9.25 (s,1H) ppm. 13C NMR (DMSO, 100 MHz): δ=27.2,
28.9, 32.3, 35.2, 50.5, 56.5, 59.2, 113.6, 115.4, 120.3, 128.6,
135.6, 156.4, 158.8, 162.4, 196.1 ppm. IR (KBr): 3438,
3375, 3195, 2963, 2195, 1684, 1649, 1512, 1454, 1371,
1253, 1215, 1144, 1120, 1040, 880 cm−1.
1H NMR (400 MHz, DMSO-d6): δ=0.96 (s, 3H), 1.05(s,
3H), 2.09–2.13 (d, J=16 Hz, 1H), 2.24–2.28 (d, J=16 Hz,
1H), 2.50–2.57 (m, 2H), 4.18 (s, 1H), 7.00 (s, 2H), 7.14–7.17
(m, 2H), 7.19–7.21 (d, J=8 Hz, 1H), 7.27–7.31 (t,, J=8 Hz,
2H) ppm. 13C NMR (DMSO, 100 MHz): δ = 27.3, 28.9,
32.3, 36, 50.4, 58.8, 113.2, 120.2, 127, 127.6, 128.8, 146.2,
158.9, 162.9, 196 ppm. IR (KBr): 3397, 3326, 3252, 3212,
2924, 2884, 2199, 1681, 1660, 1604, 1410, 1370, 1249,
1138, 1035, 697, 531 cm−1.
2.5.24 2-Amino-3-cyano-7,7-dimethyl-4-(thio-
phen-2-yl)-5-oxo-4H-5,6,7,8-tetrahydro benzopyran
1H NMR (400 MHz, DMSO-d6): δ= 1.00 (s, 3H), 1.1 (s,
3H), 2.15–2.19 (d, J=16 Hz, 1H), 2.3–2.34 (d, J=16 Hz,
1H), 2.42–2.46 (d, J=16 Hz, 1H), 2.52–2.59 (m, 1H), 4.56
(s, 1H), 6.88–6.89 (d, J = 4 Hz, 1H), 6.92–6.94 (m, 1H),
7.13 (s, 2H), 7.33–7.34 (dd, J =4 Hz, 1H) ppm. 13C NMR
(100 MHz, DMSO-d6): δ = 26.9, 29.1, 30.9, 32.2, 50.3,
58.5, 113.4, 120.1, 124.5, 124.9, 127.3, 149.8, 159.4, 163,
196 ppm. IR (KBr): 3383, 3322, 3208, 2962, 2928, 2883,
2196, 1679, 1661, 1602, 1417, 1375, 1215, 1171, 1036,
699 cm−1.
2.5.23 2-Amino-3-cyano-7,7-dimethyl-4-(4-hydroxyphenyl
)-5-oxo-4H-5,6,7,8-tetrahydro benzopyran
1H NMR (400 MHz, DMSO-d6): δ=0.95 (s, 3H), 1.04 (s,
3H), 2.07–2.11 (d, J=16 Hz, 1H), 2.22–2.26 (d, J=16 Hz,
700000
600000
3 Result and discussion
500000
400000
300000
200000
100000
0
FSM-16
3.1 Preparation of FSM‑16/AEPC‑SO3H
FSM-16/AEPC-SO3H
The procedure for the synthesis of FSM-16 was presented
in literature [25]. For the production of N-(2-aminoethyl)-
2-pyrrolidone-4-carboxylic acid (AEPC), the reaction of
itaconic acid with ethylenediamine was carried out in water
at the reflux condition [26]. Then treatment of the FSM-16
with AEPC led to production of FSM-16/AEPC. Finally, to
prepare of catalyst, chlorosulfuric acid was added to FSM-
16/AEPC (Scheme 1). Eventually, FSM-16/AEPC-SO3H
0
2
4
6
8
10
12
2theta
Fig. 3 XRD pattern of FSM-16 and FSM-16/AEPC-SO3H
Fig. 4 EDX spectrum of FSM-
16/AEPC-SO3H
1 3

M. Hajjami et al.
Fig. 5 The SEM images of FSM-16/AEPC-SO3H
was obtained and is fully characterized with FT-IR, TGA,
XRD, SEM, TEM, BET and EDX spectrum.
spectrum of FSM-16/AEPC-SO3H (c), the peaks that
appear at 3450, 2931–2892 and 1636 cm−1 can be related
to NH2 stretching vibrations, CH2 stretching and carbonyl
of amid group respectively. Additionally, the vibration
signals in region of 961–1164 cm−1 are typical SO3–H
groups [28].
3.2 Characterization of FSM‑16/AEPC‑SO3H
Figure 1 represents the FT-IR spectrum of FSM-16 (a),
FSM-16/AEPC (b) and FSM-16/AEPC-SO3H (c). The
FT-IR spectra of FSM-16 (a) indicate the band in the
802 and 1085 cm−1 region assigned to the symmetric and
asymmetric stretching modes of Si–O–Si. The another
bond in the wavenumber of 3457 cm−1 assigned to OH
stretching vibrations on the surface of FSM-16. In the
spectra of FSM-16/AEPC (b), the peak at 3449 cm−1
can be contributed to the NH2 stretching vibrations. The
vibration of stretching modes of CH2 and carbonyl of amid
group demonstrate at 2926–2979 cm−1 and 1634 cm−1
respectively. Also, the bands that appear in the 801 and
1094 cm−1 assigned to the symmetric and asymmetric
stretching modes of Si–O–Si. As shown in the FT-IR
Figure 2 shows the thermogravimetric analysis (TGA)
of FSM-16 and FSM-16/AEPC-SO3H. The TGA was used
to determinate the amount of organic groups on the surface
of FSM-16. The weight loss occurs at temperature below
100 °C that is related to the loss of solvent, adsorbed surface
hydroxyl group and water in synthesized catalyst. As shown
in Fig. 2, the total amount of organic content of synthesized
catalyst was obtained to be 10 wt% at 200–600 °C.
The XRD pattern of FSM-16 and FSM-16/AEPC-SO3H
have been recorded in Fig. 3. Diffraction peaks are observed
in the lower angle region 2θ < 10 reflections of the two
dimensional hexagonal structure of the FSM-16 material.
Due to partial loss synthesized catalyst’s ordered structure
1 3

FSM-16/AEPC-SO3H: Synthesis, Characterization and Its Application for the Catalytic…
Fig. 6 The SEM images of recovered catalyst
and the presence of organic moieties onto the mesoporous
of FSM-16, the intensity of peaks for the catalyst is lower
than FSM-16 [2].
for synthesized catalyst and FSM-16 obtain 0.71 cm3 g−1
and 1.21 cm3 g−1.
The back titration of the catalyst was applied for deter-
mination of the acid amount on the surface of synthesised
catalyst. In this light, 0.1 g of the synthesized catalyst was
added to aqueous NaCl solution (1 mol/l, 10 ml) with an ini-
tial pH 7.4. The mixture was stirred for 30 min, until the pH
of the solution had decreased to 2.81. This result indicates
ion exchange between sulfamic acid protons and sodium ions
that is equal to a loading of 0.15 mmol/g of sulfuric acid
group.
The synthesized catalyst was analyzed using EDS to
obtain the existence elements in the catalyst. As shown in
Fig. 4, the Si, O, N, C and S showed in the EDX spectrum
of FSM-16/AEPC-SO3H. Also the SEM images of FSM-16/
AEPC-SO3H and recovered catalyst indicated in Figs. 5 and
6. As shown in this Figure, nanometer-sized particles were
confirmed also the morphology of synthesized catalyst is
clear.
The transmission electron microscopy (TEM) images
of catalyst and recovered catalyst are shown in Fig. 7. The
image of FSM-16/AEPC-SO3H showed the hexagonal chan-
nels with uniform pore size. The structure of the recovered
catalyst did not change the general shape of catalyst and
no considerable shape change was observed in recovered
catalyst.
3.3 Investigation of the Catalytic Activity
of FSM‑16/AEPC‑SO3H for Multi Component
Reactions
After the characterization of catalyst and confirma-
tion of structure, we were investigated the catalyst activ-
ity in synthesis of 1,8-dioxo-octahydroxanthene and
tetrahydrobenzo[b]pyran derivatives.
Due to obtained physicochemical and structural param-
eters of FSM-16/AEPC-SO3H and FSM-16, the nitrogen
adsorption–desorption isotherms was applied (Fig. 8). The
type of nitrogen adsorption–desorption isotherm of synthe-
sized catalyst and FSM-16, based on the IUPAC classifica-
tion, are a typical type IV isotherm, which is characteristic
of mesoporous materials. Brunauer–Emmett–Teller (BET),
surface area for the synthesized catalyst and FSM-16 are
603 m2 g−1 and 1001 m2 g−1 respectively. Also total volume
In our first experiments, condensation reaction between
4-chlorobenzaldehyde (1 mol) and dimedone (2 mol) in the
presence of FSM-16/AEPC-SO3H as catalyst was chosen as
a model reaction.
During the optimization of the reaction conditions for the
synthesis of 1,8-dioxo-octahydroxanthene, we have studied
the amount of the catalyst. for this reason, the amounts of
1 3

M. Hajjami et al.
Fig. 7 TEM images of catalyst (a, b) and recovered catalyst (c, d)
0.75 mol%, 0.6 mol%, 0.45 mol%, 0.3 mol% and catalyst
free condition was investigated. The 0.45 mol% of FSM-16/
AEPC-SO3H was the best result. Also we were tested the
solvents of EtOH, H2O, PEG, CH3CN and solvent free con-
dition. As is evident from Table 1 entry 3, the best results
were achieved in the solvent-free conditions. Finally, the
1 3

FSM-16/AEPC-SO3H: Synthesis, Characterization and Its Application for the Catalytic…
40
In the obtained optimum conditions, a wide range of
aldehydes were used for synthesis of 1,8-dioxo-octahy-
droxanthene (Scheme 2). Among the various aldehydes
compounds, electron-withdrawing groups reacted faster
than electron-donating groups. The results summarized in
Table 2.
35
30
25
20
15
10
5
The suggested mechanism for the synthesis of 1,8-dioxo-
octahydroxanthene in the presence of FSM-16/AEPC-SO3H,
on the basis of the literature [32], is proposed in Scheme 3.
The condensation of the one molecule of dimedone with
activated aldehyde give intermediate (I) that with dehy-
dration, give intermediate (II). Then another molecule of
dimedone reacts with (II) by Michael addition to afford the
intermediate (III). Finally, cyclodehydration of (IV) produc
1,8-dioxo-octahydroxanthenes. As shown in Fig. 9, justi-
fication mechanism of catalyst was investigated by FT-IR
spectrum of product and intermediate.
adsorpꢀon catalyst
desorpꢀon catalyst
adsorpꢀon FSM-16
desorpꢀon FSM-16
0
0
0.2
0.4
0.6
0.8
1
1.2
Relaꢀve pressure, (P/P°)
Fig. 8 Nitrogen adsorption–desorption isotherms of FSM-16 and
FSM-16/AEPC-SO3H
Then the catalytic ability of FSM-16/AEPC-SO3H was
investigated for the synthesis of tetrahydrobenzo[b]pyran
derivatives. In this light, the one pot synthesis of 4-chlo-
robenzaldehyde (1 mol), malononitrile (1 mol) and dime-
done (1 mol) in the presence of FSM-16/AEPC-SO3H was
choosing as model reaction.
Table 1 Optimization for the synthesis of 1,8-dioxo-octahydroxan-
thene with 4-chlorobenzaldehyde, dimedone and FSM-16/AEPC-
SO3H as catalyst
Entry Catalyst (mol%) Solvent
Temperature (°C) Yield %a
Initially, we assessed the amount of catalyst. Hence the
amounts of 0.45 mol%, 0.6 mol%, 0.75 mol%, and catalyst
free conditions were applied. According to the obtained
results (Table 3, entry 3), the amount of 0.6 mol% of syn-
thesized catalyst, produced the high yield.
1
2
3
4
5
6
7
8
0
0.3
0.45
0.6
0.75
0.45
0.45
0.45
0.45
0.45
0.45
30 gb
Solvent-free 120
28
77
88
85
88
23
31
37
43
54
87
38
Solvent-free 120
Solvent-free 120
Solvent-free 120
Solvent-free 120
Then, we screened different solvents for the synthesis of
2-amino-4-(4-chlorophenyl)-3-cyano-7,7-dimethyl-5-oxo-
4H-5,6,7,8 tetrahydro-benzo[b]pyran. As shown in Table 3,
the mixture of H2O:EtOH with ratio of 3:1 ml resulted in
the highest yield. In order to demonstrate the effect of tem-
perature on the synthesis of tetrahydrobenzo[b]pyran, we
tested temperatures of 60, 80 and 100 °C. The temperature
of 80 °C was choosen.
EtOH
H2O
PEG
Reflux
Reflux
120
9
CH3CN
Reflux
10
11
12
Solvent-free 100
Solvent-free 130
Solvent-free 120
4-Chlorobenzaldehyde (1 mol), dimedone (2 mol), 15 min
aPure yield
Having established the reaction conditions, treat-
ment of many aldehydes (1 mol) with malononitrile
(1 mol) and dimedone (1 mol) in the presence of FSM-16/
AEPC-SO3H (0.6 mol%) in H2O: EtOH (ratio of 3:1 ml)
at 80 °C to generate tetrahydrobenzo[b]pyran derivatives
(Scheme 4). The activity of aldehydes compounds in syn-
thesis of tetrahydrobenzo[b]pyran is very important. As
shown in Table 4 among the various aldehydes compounds,
bThe reaction catalyst by FSM-16/AEPC
temperature effect on the model reaction checked. The
results show that temperature of 120 °C is the best (Table 1,
entry 3).
Scheme 2 General reaction
X
for the synthesis of 1,8-dioxo-
octahydroxanthene
O
CHO
O
O
FSM-16/AEPC-SO3H
Solvent free, 120°C
+ 2
O
X
O
1 3

M. Hajjami et al.
Table 2 One-pot synthesis of
1,8-dioxo-octahydroxanthene
derivatives catalyzed by FSM-
16/AEPC-SO3H
Entry
1
Aldehyde
Time (min)
15
Yield (%)a
88
M.p (°C)
228–230
References
[29]
CHO
Cl
2
3
4
5
6
20
30
30
35
45
84
86
89
86
77
235–237
222–224
243–245
181–183
162–164
[30]
[31]
[7]
CHO
Br
CHO
F
CHO
OMe
[32]
[8]
CHO
OMe
OMe
CHO
NO2
7
8
95
90
75
70
222–224
247–250
[32]
[29]
CHO
OH
CHO
OH
9
30
20
80
64
241–243
249–252
[32]
[8]
CHO
Cl
Cl
10
CHO
NO2
1 3

FSM-16/AEPC-SO3H: Synthesis, Characterization and Its Application for the Catalytic…
Table 2 (continued)
Entry
11
Aldehyde
Time (min)
15
Yield (%)a
88
M.p (°C)
224–226
References
[29]
CHO
NO2
Aldehyde (1 mol), dimedone (2 mol), FSM-16/AEPC-SO3H (0.45 mol%), Solvent-free at 120 °C
aPure yield
O
S
R
O
O
H
O
H
H
H
O
O
O
S
O
O
H
H
O
O
O
R
R
I
O
H
H2O
H
O
R
O
H
R
O
R
R
OH+
O
O
OH
HO
O
O
O
HO
O H
S O
O
III
IV
II
H2O
O
O
O
S
O
N
=
H
O
O
O
O
NHSO3H
O
S
O
O
+
H
O
Scheme 3 Mechanism suggested for synthesis of 1,8-dioxo-octahydroxanthenes catalyzed by FSM-16/AEPC-SO3H
1 3

M. Hajjami et al.
Fig. 9 FT-IR spectrum of
intermediate and product of
1,8-dioxo-octahydroxanthenes
Table 3 Optimization
for the synthesis of
Entry
Catalyst (mol%)
Solvent
Temperature (°C)
Yield%a
H2O: EtOHb
H2O: EtOHb
H2O: EtOHb
H2O: EtOHb
Solvent-free
EtOH
80
80
80
80
80
Reflux
80
80
60
56
69
89
90
49
43
44
54
46
92
58
tetrahydrobenzo[b]pyran
with 4-chlorobenzaldehyde,
malononitrile, dimedone and
FSM-16/AEPC-SO3H as
catalyst
1
2
3
4
5
6
7
8
0
0.45
0.6
0.75
0.6
0.6
0.6
0.6
0.6
0.6
40 gc
H2O
PEG
9
10
11
H2O: EtOHb
H2O: EtOHb
H2O: EtOHb
100
80
4-chlorobenzaldehyde (1 mol), malononitrile (1 mol), dimedone (1 mol), 30 min
aPure yield
bRatio: 3:1 ml
cThe reaction catalyst by FSM-16/AEPC
1 3

FSM-16/AEPC-SO3H: Synthesis, Characterization and Its Application for the Catalytic…
Scheme 4 General reaction for
synthesis of tetrahydrobenzo[b]
pyran
X
CHO
O
O
CN
CN
CN
FSM-16/AEPC-SO3H
+
+
O
O
NH2
X
H2O/EtOH (3:1)
80°C
Table 4 One-pot synthesis of
tetrahydrobenzo[b]pyran with
aldehyde, malononitrile and
dimedone catalyzed by FSM-
16/AEPC-SO3H
Entry
1
Aldehyde
Time (min)
30
Yield (%)a
89
M.p (°C)
References
[20]
211
CHO
Cl
2
3
4
45
35
30
85
81
87
197–200
185–189
174–179
[33]
[21]
[34]
CHO
Br
CHO
F
CHO
NO2
5
35
80
205–208
[35]
CHO
NO2
6
7
30
88
84
226–230
198–200
[23]
[21]
CHO
NO2
120
CHO
OMe
8
240
68
180–184
[36]
CHO
OMe
OMe
1 3

M. Hajjami et al.
Table 4 (continued)
Entry
9
Aldehyde
Time (min)
180
Yield (%)a
62
M.p (°C)
215–218
References
[37]
CHO
Me
10
25
88
119–122
[37]
CHO
Cl
Cl
11
12
60
89
65
223–227
207–208
[20]
[21]
CHO
135
CHO
OH
13
55
80
215–217
[21]
CHO
S
Aldehyde (1 mol), malononitrile (1 mol), dimedone (1 mol), FSM-16/AEPC-SO3H (0.6 mol%) in H2O:
EtOH (3:1 ml) at 80 °C
aPure yield
electron-withdrawing groups reacted faster than electron-
donating groups and also the yields of product were bet-
ter. When aldehydes containing an electron-donating group
were used (Table 4, entries 7–9 and 12), the corresponding
tetrahydrobenzo[b]pyran was produced in moderate to good
yields, but the reaction time was longer compared to alde-
hydes with electron withdrawing groups. The results are in
Table 4.
3.4 Reusability of the FSM‑16/AEPC‑SO3H
For practical purposes, the reusability of the catalyst is
highly favorable. In this light, the reusability of FSM-16/
AEPC-SO3H was tested for synthesis of 2-amino-4-(4-
chlorophenyl)-3-cyano-7,7-dimethyl-5-oxo-4H-5,6,7,8-tet-
rahydro-benzo[b]pyran. After the completion of the reaction,
the reaction mixture was cooled to room temperature and
washed by H2O. Then hot EtOH was added and centrifuged.
The remaining catalyst was washed, dried and applied for the
next run. The results were indicated that the heterogeneous
catalysis of FSM-16/AEPC-SO3H has reusability for at least
five times (Fig. 11).
A possible mechanism for the synthesis of
tetrahydrobenzo[b]pyran catalyzed by FSM-16/AEPC-SO3H
is indicated in Scheme 5 [38]. As shown in this Scheme 5,
malononitrile first condenses with activated aldehyde fol-
lowed by dehydration to afford arylidenemalononitrile inter-
mediate (I). Subsequently, the nucleophilic addition of the
enolizable dimedone to the arylidenemalononitrile interme-
diate (I) followed by consecutive intramolecular cyclization
occur to afford the intermediate (IV) which rearranges to
afford the expected tetrahydrobenzo[b]pyran.
To extend the scope of merit of synthesised catalyst, the
FSM-16/AEPC-SO3H was compared with other catalysts for
synthesis of 2-amino-4-(4-chlorophenyl)-3-cyano-7,7-dime-
thyl-5-oxo-4H-5,6,7,8-tetrahydro-benzo[b]pyran (Table 5,
entry 1–7) and 3,3,6,6-tetramethyl-9-(4-chloro-phenyl)-
1,8-dioxo octahydroxanthene (Table 5, entry 8–11).
Also in Fig. 10, FT-IR spectrum of intermediates and
product of tetrahydrobenzo[b]pyran indicated.
1 3

FSM-16/AEPC-SO3H: Synthesis, Characterization and Its Application for the Catalytic…
O2
S
O2
Ar
CN
O H
S O H
HO
CN
NH
N
C
C
-H2O
CN
CN
Ar
CN
CN
Ar
H
H
H
I
O
O
O
S
O
O2
S O H
O
Ar
O
H
O
H
CN
CN
N
C
O
S
O
O
O
Ar
H
H
CN
O2
S O H
O
II
O
O
Ar
O
O
Ar
O
O
Ar
H
CN
CN
C N
CN
N
NH2
OH
H
O
O2
O2S
S O H
IV
III
O
O
O
S
O
O
N
=
H
O
NHSO3H
Scheme 5 The possible mechanism for the synthesis of tetrahydrobenzo[b]pyran
1 3

M. Hajjami et al.
Fig. 10 FT-IR spectrum of
intermediates (a, b) and product
of tetrahydrobenzo[b]pyran (c)
4 Conclusion
In summary, we have developed a new, efficient and
heterogonous catalyst of FSM-16/AEPC-SO3H for the
one pot synthesis of 1,8-dioxo-octahydroxanthene and
tetrahydrobenzo[b]pyran derivatives. The prepared cata-
lyst was confirmed by several analyses including: FT-IR,
TGA, XRD, SEM, TEM, EDS and BET techniques. The
advantages of this method are: utilization of green solvent
and solvent free condition, short time reaction, high yield
of products, simple work-up and purification, simple sepa-
ration of catalyst and reusability of catalyst for five time.
81
61
41
21
1
5
4
3
2
1
Run number
Fig. 11 The reusability of the FSM-16/AEPC-SO3H
1 3

FSM-16/AEPC-SO3H: Synthesis, Characterization and Its Application for the Catalytic…
Table 5 Comparison results of FSM-16/AEPC-SO
3H with other catalysts
Entry
Conditions
Time (min)
Yield%
References
1
2
3
4
5
6
10 wt% CaHPO4 ,H2O/EtOH(4:1), 80 °Ca
[Ch][OH], H2O, 80 °Ca
120
60
20
60
25
92
86
90
95
90
95/97
[23]
[21]
[37]
[38]
[39]
[40]
SiO2–Pr–SO3H, H2O, refluxa
Fe3-xTixO4@SO3HNPs (0.03 g), EtOH (3 ml)/H2O (3 ml), refluxa
Fe3O4@SiO2/DABCO (0.05 g), H2O, 80 °Ca
Fe3O4@SiO2-imid-PMA n(0.02 g), H2O, reflux or H2O, ultrasonic irradia- 10/5
tion (40 kHz), r.t, Fe3O4@SiO2-imid-PMAn(0.015 g)a
7
8
9
10
11
FSM-16/AEPC-SO3H(0.6 mmol%),H2O/EtOH (3:1), 80 °Ca
Fe3O4@SiO2Imid-PMAn (0.03 g), EtOH (5 ml), refluxb
Magnetic nanoparticles Fe3O4 (0.01 mmol), H2O (5 ml), 80 °Cb
Fe3O4/SiO2-Propyl-Pip-SO3H (0.05 g), SFC, 120 °Cc
FSM-16/AEPC-SO3H (0.45 mmol%), solvent free, 120 °Cb
30
60
33
30
15
89
91
90
89
88
This work
[41]
[42]
[43]
This work
aReaction of 4-chlorobenzaldehyde, dimedone and malononitrile for the synthesis of tetrahydrobenzo[b]pyran
bReaction of 4-chlorobenzaldehyde and dimedone for the synthesis of 1,8 dioxooctahydro xanthene
cReaction of 4-chlorobenzaldehyde and 3,5-Xylenol for the synthesis of 9H-xanthene
16. Li GC (2008) J Chem Res 1:484
Acknowledgements Financial support for this work by the Ilam Uni-
versity, Ilam, Iran is gratefully acknowledged. The Natural Sciences
and Engineering Research Council of Canada is gratefully acknowl-
edged for support (RHEH).
17. Zhang ZH, Zhang P, Yang SH, Wang HJ, Deng J (2010) J Chem
Sci 122:427
18. Davoodnia A, Yadegarian S, Nakhaei A, Tavakoli-Hoseini N
(2016) Russ J Gen Chem 86:2849
19. Maleki A, Aghaei M, Ghamari N (2016) Appl Organomet Chem
30:939
Compliance with Ethical Standards
20. Kshirsagar AK, Bankar SS, Khandebharad AU, Sarda SR, Soni
MG, Agrawal BR (2016) J Med Chem Drug Discov 1:720
21. Hu H, Qiu F, Ying A, Yang J, Meng H (2014) Int J Mol Sci
15:6897
Conflict of interest Authors declare that there is no conflict of interest
involved.
22. Azarifar D, Khatami SM, Zolfigol MA, NejatYami R (2014) J Iran
Chem Soc 11:1223
References
23. Bodaghifard MA, Solimannejad M, Asadbegi S, Dolatabadifara-
hani S (2016) Res Chem Intermed 42:1165
1. Nagata H, Takimura M, Yamasaki Y, Nakahira A (2006) Mater
Trans 47:2103
24. Zhang P, Yu YD, Zhang ZH (2008) Synth Commun 38:4474
25. Matsumoto A, Sasaki T, Nishimiya N, Tsutsumi K (2002) Col-
loids Surf A 203:185
2. Jakdetchai O, Takayama N, Nakajima T (2005) Kinet Catal 46:56
3. Das P, Silva AR, Carvalho AP, Pires J, Freire C (2009) Catal Lett
129:367
26. Qi P, Chen HL, Nguyen HTH, Lin CC, Miller SA (2016) Green
Chem 18:4170
4. Das P, Silva AR, Carvalho AP, Pires J, Freire C (2008) Colloid
Surf A 329:190
27. Zolfigol MA, Madrakian E, Ghaemi E (2002) Molecules 7:734
28. Hajjami M, Tahmasbi B (2015) RSC Adv 5:59194
29. Lu HY, Li JJ, Zhang ZH (2009) Appl Organomet Chem 23:165
30. Bayat M, Imanieh H, Hossieni SH (2009) Chin J Chem 27:2203
31. Nisar M, Ali I, Shah MR, Badshah A, Qayum M, Khan H, Khan
I, Ali S (2013) RSC Adv 3:21753
5. Medway AM, Sperry J (2014) Green Chem 16:2084
6. Quadri SA, Das TC, Malik MS, Seddigi ZS, Farooqui M (2016)
Chem Select 1:4602
7. Makone S, Mahurkar S (2013) Green Sustain Chem 3:27
8. Arbosara FS, Shirini F, Abedini M, Moafi HF (2015) J Nanostruct
Chem 5:55
32. Hazeri N, Masoumnia A, Mghsoodlou MT, Salahi S, Kangani
M, Kianpour S, Kiaee S, Abonajmi J (2015) Res Chem Intermed
41:4123
9. Javid A, Heravi MM, Bamoharram FF (2011) J Chem 8:910
10. Kahandal SS, Burange AS, Kale SR, Prinsen P, Luque R, Jayaram
RV (2017) Catal Commun 97:138
33. Sheikhhosseini E, Ghazanfari D, Nezamabadi V (2013) Iran J
Catal 3:197
11. Sadat SN, Hatamjafari F (2015) Orient J Chem 31:1191
12. Zare A, Moosavi-Zare AR, Merajoddin M, Zolfigol MA, Hekmat-
Zadeh T, Hasaninejad A, Khazaei A, Mokhlesi M, Khakyzadeh
V, Derakhshan-Panah F, Beyzavi MH, Rostami E, Arghoon A,
Roohandeh R (2012) J Mol Liq 167:69
34. Beheshtiha S, Oskoole H, Pourebrahimi F, Zadsirjan V (2015)
Chem Sci Trans 4:689
35. Montazeri N, Noghani T, Ghorchibeigy M, Zoghi R (2014) J
Chem 2014:1
36. Lu J, Fu XW, Zhang G, Wang C (2016) Res Chem Intermed
42:417
13. Kumbhar A, Kamble S, Rashinkar G, Mote K, Salunkhe R (2010)
Arch Appl Sci Res 2:235
37. Ziarani GM, Abbasi A, Badiei A, Aslani Z (2011) J Chem 8:293
38. Azarifar D, Abbasi Y (2016) Synth Commun 46:745
39. Davarpanah J, Kiasat AR, Noorizadeh S, Ghahremani M (2013)
J Mol Catal A 376:78
14. Li JJ, Tao XY, Zhang ZH (2008) Phosphorus Sulfur Silicon
183:1672
15. dos Santos WH, Da Silva-Filho LC (2016) Chem Pap 70:1658
1 3

M. Hajjami et al.
40. Esmaeilpour M, Javidi J, Dehghani F, Nowroozi Dodeji F (2015)
RSC Adv 5:34:26625
42. Karami B, Hoseini SJ, Eskandari K, Ghasemib A, Nasrabadi H
(2012) Catal Sci Technol 2:331
41. Esmaeilpour M, Javidi J, Dehghani F, Nowroozi Dodeji F (2014)
New J Chem 38:5453
43. Mobinikhaledi A, Khajeh-Amiri A (2014) React Kinet Mech Catal
112:131
1 3