Efficient synthesis of multiply substituted furans using BF?Propyl/dopamine/Pd as a green catalyst

Article abstract of DOI:10.1002/aoc.5530

One of the commonly used methods to synthesize furans is the three-component reaction among aromatic aldehyde, arylamine, and acetylenedicarboxylate. The main advantages of this work are easy reaction work-up, short reaction time, high yield and easy recyclability, reusability of the catalyst. And also basalt fiber applications are surely innovative in many industrial and economic fields, because of its good mechanical, chemical and thermal performances.

Full text of DOI:10.1002/aoc.5530

Received: 23 November 2019
DOI: 10.1002/aoc.5530
Revised: 15 December 2019
Accepted: 20 December 2019
F U L L P A P E R
Efficient synthesis of multiply substituted furans using
BF@Propyl/dopamine/Pd as a green catalyst
Zahra Karamshahi
| Ramin Ghorbani-Vaghei
Department of Organic Chemistry,
Faculty of Chemistry, Bu-Ali Sina
University, Hamedan, 6517838683, Iran
One of the commonly used methods to synthesize furans is the three-compo-
nent
reaction
among
aromatic
aldehyde,
arylamine,
and
acetylenedicarboxylate. The main advantages of this work are easy reaction
work-up, short reaction time, high yield and easy recyclability, reusability of
the catalyst. And also basalt fiber applications are surely innovative in many
industrial and economic fields, because of its good mechanical, chemical and
thermal performances.
Correspondence
Ramin Ghorbani-Vaghei, Department of
Organic Chemistry, Faculty of Chemistry,
Bu-Ali Sina University. Hamedan,
6517838683, Iran.
Email: rgvaghei@yahoo.com
K E Y W O R D S
basalt fibers, dimethyl acetylenedicarboxylate, furan, green, palladium
1 | INTRODUCTION
In the last few years, the synthesis of N-heterocycles
because of varied biological and pharmaceutical usages
The catalyst support must have good surface cohesion to
coat the various reagents and be chemically stable to the
reactive environment.[1,2]
The usage of basalt fibers (BFs) as ceramic supports has
significant potential in terms of cost and approachability of
crude materials. Basalt is a natural material that exists in
volcanic stones obtained from frozen lava.[3–5]
has been increasingly studied.[11–13]
Furan and its end product, obtained from synthetic in
addition to natural resources, have attracted much atten-
tion with extensive varieties of medicine usages.[14,15]
These skeletons display several biological activities such
as antimicrobial,[16–19] antifungal,[20] anti-inflammatory,[21,22]
anticancer[23,24] and anti-viral HIV-1[25] activities.
The form BFs is similar to glasslike filaments 4.5 to
Moreover, furans show pervasive synthetic building
blocks capable of experiencing a range of transformations
such as cycloaddition reactions that proceed with
dearomatization of the furan moiety, resulting in the
quick creation of molecular complexity.[26–28]
Some strategies have been devised to access furans
bearing different substitution patterns, such as the Feist-
Benary condensation of β-dicarbonyl derivatives with α-
substituted ketones[29,30] For this vast variety of suffi-
ciency and usability, different methods toward replaced
7 cm in length and 1.5 to 6 μm in diameter. They are
ꢀ
thermally stable to melting up to 950 С, keep resistance
ꢀ
to mechanical deformation up to 700 С, and possesses
high chemical stability. The basalt fiber consists of sev-
eral metal oxides, such as those of Na, K, Ca, Mg, Al, Si,
Fe, and Ti.[5] By chemical compositions analysis, it can be
seen that SiO2 is the major constituent and Al2O3 is the
second constituent.[4,6–8]
The development and increasing application of basalt
fibers are due to its useful properties such as high modu-
lus and strength also remarkable heat resistance and
notable vibration isolators. The growing use of basalt
fiber brought up the question if basalt fiber is dangerous
to health. Basalt looks to be harmless, as a result of differ-
ent morphology and surface properties prevent any carci-
nogenic or poisonousness effects, which are shown by
asbestos instead.[3,9,10]
furans have been extended, which involve the use of Pd
(Ph3P)2Cl2,[19] Al (HSO4)3
Iron (III) chloride[31] and
,[25]
lactic acid.[32] Other approaches suffer from one of the
following problems: low yields, long reaction times, waste
pollution, harsh reaction conditions, and tiresome
work-up.
The current study concentrates on the usage of basalt
fibers as stable, inert, eco-friendly catalyst for synthesis of
Appl Organometal Chem. 2020;e5530.
wileyonlinelibrary.com/journal/aoc
© 2020 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.5530

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KARAMSHAHI AND GHORBANI-VAGHEI
furan byproducts with yield improved and reduce reac-
tion period (Scheme 1).
Then (3-chloropropyl)triethoxysilane (2.0 ml) was added
and the mixture was refluxed at 110 ꢀC with constant stir-
ring conditions for 24 hr. After the reaction time was
completed, the reaction mixture (BF@Propyl) was col-
lected and separated by centrifugation, then washed with
toluene and ethanol for several times. Finally, the
resulting functionalized BF@Propyl was dried at 80 ꢀC.
2 | EXPERIMENTAL
2.1 | General information and methods
All chemicals were purchased from commercial suppliers
(Merck and Fluka companies). Proton Nuclear Magnetic
Resonance NMR (1H NMR) spectra and carbon nuclear
magnetic resonance (13C NMR) spectra were entered on
Bruker BioSpin GmbH 400 MHz FT NMR spectrometers.
Infrared (IR) spectra were taken using a Shimadzu
435-U-04 FT spectrophotometer from KBr tablets. IR data
are represented as the frequency of absorption (cm−1).
Melting points were measured on a BUCHI 510 apparatus
in open capillary tubes. Scanning electron microscopy
(SEM) was fulfilled med on EM3200 instrument operated
at 30 kV accelerating voltage. The structure of the new
BF@Propyl/dopamine/Pd was characterized using XRD,
IR, SEM, EDX and TGA analysis. Energy dispersive X-ray
(EDX) and Scanning electron microscopy (SEM) analysis
of the prepared catalyst was fulfilled on a FESEM-SIGM
(Germany) instrument. Thermo-gravimetric analysis
(TGA) was accomplished on a DUPONT 951 TA
Instruments.[33]
2.4 | Preparation of
BF@propyl/dopamine
BF@Propyl (1 g) was added to 50 ml of toluene and was
dispersed using an ultrasonic bath for 20 min. Subse-
quently, 2-(3,4-dihydroxyphenyl)ethyleneamine (dopa-
mine; 3 g) was added and refluxing for 24 hr. After this
time, the basalt fiber coated with dopamine was synthe-
sized and separated by filter paper. In the separation and
purification step, the precipitate was washed with toluene
and then water, then dried at 100 ꢀC.
2.5 | Preparation of
BF@propyl/dopamine/Pd
PdCl2 (1 mmol) (dissolved in 10 ml of acetonitrile) to
0.5 g BF@Propyl/dopamine (dispersed in acetonitrile
using an ultrasonic bath for 15 min) added. The reaction
ꢀ
mixture was stirred at 90 C for 24 hr. The precꢀipitate
2.2 | Preparation of surface modification
of BF
was washed with acetone and then dried at 50 C for
18 hr (Scheme 2).[35]
Before the linkage an organic/inorganic coverage
(propyl/dopamine/nanoparticle Pd) on the basalt fiber,
crude basalt fibers were washed with acetone and dried
under vacuum for 1 hr to remove the agent on the level
and then behaved with piranha solution (H2SO4:H2O2 (v/
2.6 | General procedure for the synthesis
of furans
Aromatic aldehyde (1.0 mmol), aryl amine (1.0 mmol),
ꢀ
v) =7:3) at 90 C for 1 hr to produce more active silanol
acetylenedicarboxylate (1.0 mmol) and 0.06
g
groups on the BF surface. Afterward, the basalt fibers
prepared from the previous step were combined with 1 M
BF@Propyl/dopamine/Pd nanocatalyst in EtOH (5 ml)
was heated at 80 ꢀC. After the completion of the reaction
as indicated by the TLC (n-hexane/acetone 10:2), the
reaction mixture was cooled to room temperature and fil-
tered to eliminate the catalyst. The crude product washed
with ethanol and purified by hot ethanol. The products
were characterized using physical and spectroscopic (IR,
NMR, MS) data. (Supporting Information 1-3).
ꢀ
HCl solution at 40 C for 1 hr. Finally, it was washed
with deionized water and dried in an oven at 100 ꢀC.[34]
2.3 | Preparation of BF@propyl
Basalt fiber (1 g) synthesized in the previous step was
added to a flask containing 50 ml of toluene was added.
2.7 | Evaluation of palladium removal
from BF@propyl/dopamine/Pd catalyst
surface in furan synthesis
Methyl-5-oxo-2-phenyl-4-(phenylamino)-2,-
SCHEME 1 General synthesis of furans
5-dihydrofuran-3-carboxylate derivative (4a) was selected

EFFICIENT SYNTHESIS OF MULTIPLY SUBSTITUTED FURANS
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SCHEME 2 BF@Propyl/dopamine/Pd structure
as the sample for this test. After 50 per cent reaction pro-
gress (35 min), the reaction was stopped and the catalyst
was separated from the reaction mixture by centrifuga-
tion. The reaction mixture was placed under the same
conditions for 30 min after separation of the catalyst and
no significant progress was observed in the reaction pro-
cess. The results of this test showed that palladium
nanoparticles were not released in the reaction medium
and remained on the surface of the catalyst and as well
as the catalyst was very stable in contrast to moisture, air
and reaction conditions.[36]
3H, CH3), 3.58 (s, 3H, OCH3), 6.00 (s, 1H, CH), 7.06 (m,
2H, Ar-H), 7.20–7.49 (m, 7H, Ar-H), 11.70 (s, 1H, NH);
13C NMR (125 MHz, DMSO-d6): δC (ppm) 20.3, 51.0,
60.6, 111.7, 122.5, 127.6, 128.2, 129.0, 129.1, 136.2, 133.7,
134.6, 136.5, 152.6, 162.4, 163.7; MS (m/z): 323.1 (M+),
291.1, 264.1, 236.1, 214.0, 189.1, 158.0, 130.0 (100%),
102.0, 77.0, 51.1.
2.8.3 | Methyl 2-(4-fluorophenyl)-5-oxo-
4-(phenylamino)-2,5-dihydrofuran-
3-carboxylate 4c
2.8 | Analytical data of the selected
products
White solid; M.p. 186–188 ꢀC; FT-IR (KBr) υ¯ (cm−1):
3171, 2955, 1685, 1600, 1510, 1379, 1231, 1003; H NMR
1
(500 MHz, DMSO-d6): δH (ppm) 3.57 (s, 3H, OCH3), 6.09
(s, 1H, CH), 7.02 (m, 3H, Ar-H), 7.28 (m, 4H, Ar-H), 7.54
(m, 2H, Ar-H), 11.64 (s, 1H, NH); 13C NMR (125 MHz,
DMSO-d6): δC (ppm) 59.7, 60.0, 111.6, 115.1, 122.5, 122.6,
125.5, 128.6, 129.7, 132.6, 136.0, 152.6, 160.5, 162.4, 163.8;
MS (m/z): 327.1 (M+, 100%), 295.0, 268.1, 240.1, 207.0,
170.1, 148.0, 120.0, 99.2, 77.1, 51.1.
2.8.1 | Methyl 5-oxo-2-phenyl-
4-(phenylamino)-2,5-dihydrofuran-
3-carboxylate 4a
Light yellow solid; M.p. 186–189 ꢀC; FT-IR (KBr): υ¯
(cm−1) 3262, 3210, 2958, 1702, 1681, 1499, 1383, 1234,
1
1136; H NMR (DMSO-d6, 500 MHz): δH (ppm) 3.57 (s,
3H, OCH3), 6.05 (s, 1H, CH), 7.07 (m, 1H, Ar-H), 7.23 (m,
7H, Ar-H), 7.54 (m, 2H, Ar-H), 11.73 (s, 1H, NH); 13C
NMR (125 MHz, DMSO-d6): δC (ppm) 51.0, 60.4, 111.9,
122.4, 127.6, 128.1, 128.6, 136.2, 136.4, 152.5, 162.4, 169.3;
MS (m/z): 309.1 (M+, 100%), 277.0, 250.1, 222.1, 189.1,
158.0, 130.1, 102.1, 77.1, 51.1.
2.8.4 | Methyl 2-(2-chlorophenyl)-5-oxo-
4-(phenylamino)-2,5-dihydrofuran-
3-carboxylate 4d
White solid; M.p. 214–216 ꢀC; FT-IR (KBr) υ¯ (cm−1):
3302, 3066, 2958, 1719, 1687, 1658, 1499, 1367, 1257,
1
1189, 1131; H NMR (500 MHz, DMSO-d6): δH (ppm)
2.8.2 | Methyl 5-oxo-2-phenyl-4-(p-
tolylamino)-2,5-dihydrofuran-3-carboxylate
4b
3.56 (s, 3H, OCH3), 6.41 (s, 1H, CH), 7.03 (m, 1H,
Ar-H),7.15–7.29 (m, 5H, Ar-H), 7.44 (m, 3H, Ar-H),
11.89 (s, 1H, NH); 13C NMR (125 MHz, DMSO-d6): δC
(ppm) 51.0, 56.6, 111.5, 122.3, 128.7, 129.3, 133.9,
134.4, 136.0, 153.3, 162.2, 164.0; MS (m/z): 343.1 (M+,
100%), 311.1, 284.1, 248.1, 214.1, 192.0, 164.1, 136.0,
101.1, 77.1, 51.1.
White solid; M.p. 185–187 ꢀC; FT-IR (KBr): υ¯ (cm−1
)
3231, 3064, 2955, 1706, 1680, 1515, 1467, 1382, 1201,
1
1038; H NMR (500 MHz, DMSO-d6) δH (ppm): 2.17 (s,

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KARAMSHAHI AND GHORBANI-VAGHEI
2.8.5 | Methyl 2-(2-chlorophenyl)-5-oxo-
4-(p-tolylamino)-2,5-dihydrofuran-
3-carboxylate 4e
CH3), 3.37 (s, 3H, OCH3), 6.18 (s, 1H, CH), 6.81 (s,
1H, NH), 7.05 (m, 4H, Ar-H),7.33 (m, 2H, Ar-H), 7.45
(m, 1H, Ar-H); 13C NMR (125 MHz, DMSO-d6): δC
(ppm) 20.4, 50.0, 59.0, 122.0, 125.0, 127.3, 129.0, 129.1,
132.2, 134.4, 165.9, 167.5, 168.8; MS (m/z): 401 (M+),
387.2 (100%), 340.2, 293.1, 227.2, 189.2, 149.1, 95.1,
43.1.
White solid; M.p. 206–209 ꢀC; FT-IR (KBr): υ¯ (cm−1):
3212, 2949, 1713, 1675, 1514, 1381, 1292, 1230, 1197,
1135; 1H NMR (400 MHz, CDCl3): δH (ppm) 2.25 (s,
3H, CH3), 3.74 (s, 3H, OCH3), 6.42 (s, 1H, CH),
6.98–7.10 (m, 5H, Ar-H), 7.38 (m, 3H, Ar-H), 9.13 (s,
1H, NH); 13C NMR (100 MHz, CDCl3): δC (ppm) 20.9,
52.1, 56.7, 121.8, 126.9, 127.4, 129.6,129.8 132.7, 133.3,
134.9, 135.8, 156.8, 162.7, 165.1; MS (m/z): 357.3 (M+,
100%), 325.3, 290.3, 262.3, 228.3, 192.2, 164.2, 133.3,
91.3, 65.2, 41.3.
2.8.8 | Methyl 2-(2-bromophenyl)-
4-((4-methoxyphenyl)amino)-5-oxo-
2,5-dihydrofuran-3-carboxylate 4 h
White solid; M.p. 185–187 ꢀC; FT-IR (KBr): υ¯ (cm−1):
3194, 2952, 1713, 1676, 1513, 1458, 1382, 1252, 1181,
1
1028; H NMR (500 MHz, DMSO-d6): δH (ppm) 3.54 (s,
2.8.6 | Methyl 2-(2-chlorophenyl)-
4-((4-methoxyphenyl)amino)-5-oxo-
2,5-dihydrofuran-3-carboxylate 4f
3H, OCH3), 3.67 (s, 3H, OCH3), 6.27 (s, 1H, CH), 6.83 (m,
3H, NH, Ar-H), 7.09 (m, 1H, Ar-H),7.29 (m, 3H, Ar-H),
7.48 (m, 2H, Ar-H); 13C NMR (125 MHz, DMSO-d6): δC
(ppm) 51.0, 55.1, 57.0, 111.2, 113.8, 124.4, 128.8, 129.3,
134.0, 134.4, 153.5, 157.0, 162.2, 163.8; MS (m/z): 417.1
(M+), 387.0, 340.0, 306.1, 278.1, 247.1, 210.1, 180.0, 149.1
(100%), 101.0, 75.1, 43.1.
White solid; M.p. 192–194 ꢀC; FT-IR (KBr): υ¯ (cm−1):
3177, 2955, 1709, 1679, 1514, 1391, 1252, 1137, 1000;
1H NMR (300 MHz, CDCl3): δH (ppm) 3.73 (s, 6H,
OCH3), 6.38 (s, 1H, CH), 6.79–6.81 (m, 2H, Ar-H), 6.97
(m, 1H, Ar-H), 7.16 (m, 2H, Ar-H), 7.27–7.38 (m, 3H,
Ar-H), 9.07 (s, 1H, NH); 13C NMR (75 MHz, CDCl3):
δC (ppm) 54.4, 56.2, 56.8, 113.5, 114.9, 122.8, 124.0,
124.6, 126.5, 127.6, 128.8, 130.7, 132.6, 157.1, 162.5,
165.2; MS (m/z): 373 (M+), 341, 306, 278, 245,
230, 210, 192, 178, 164, 149 (100%), 134, 115,
101, 83, 69, 55, 41.
2.8.9 | Methyl 2-(2-nitrophenyl)-5-oxo-
4-(p-tolylamino)-2,5-dihydrofuran-
3-carboxylate 4i
White solid; M.p. 198–201 ꢀC; FT-IR (KBr): υ¯ (cm−1):
3177, 3064, 2955, 1710, 1684, 1639, 1526, 1385, 1201,
1
1105, 1038; H NMR (500 MHz, DMSO-d6): δH (ppm)
2.19 (s, 3H, CH3), 3.50 (s, 3H, OCH3), 6.77 (s, 1H,
CH), 7.12 (m, 3H, Ar-H), 7.51 (m, 4H, Ar-H),7.86 (m,
1H, Ar-H), 11.98 (s, 1H, NH); 13C NMR (125 MHz,
DMSO-d6): δC (ppm) 20.1, 50.9, 54.4, 111.0, 122.0,
122.1, 124.6, 127.3, 129.3, 131.0, 133.6, 135.0, 150.1,
153.6, 156.9, 162.2, 164.2; MS (m/z): 368.1 (M+), 345.1,
322.1, 277.1, 247.1, 207.1 (100%), 175.1, 134.1, 91.1,
65.1, 41.1.
2.8.7 | Methyl 2-(2-bromophenyl)-5-oxo-
4-(p-tolylamino)-2,5-dihydrofuran-
3-carboxylate 4 g
White solid; M.p. 205–208 ꢀC; FT-IR (KBr): υ¯ (cm−1):
3354, 2912, 1690, 1538, 1514, 1383, 1242, 1154, 1029;
1H NMR (500 MHz, DMSO-d6): δH (ppm) 2.18 (s, 3H,
TABLE 1 Optimization of reaction conditionsa
Entry
Catalyst (g)
0.05
Solvent
-
Temperature (ꢀC)
Time (min)
Yield (%)b
1
2
3
4
5
110
720
1440
720
65
15
20
40
82
86
0.05
H2O/EtOH
CH3CN
EtOH
100
0.05
Reflux
Reflux
Reflux
0.05
0.06
EtOH
65
aReaction conditions: benzaldehyde (1 mmol), aniline (1 mmol), dimethyl acetylenedicarboxylate (1 mmol), catalyst, solvent (5 mL).
bIsolated yield.

EFFICIENT SYNTHESIS OF MULTIPLY SUBSTITUTED FURANS
5 of 10
TABLE 2 Synthesis of furan derivatives using BF@Propyl/dopamine/Pd as a green catalysta
(Continues)

6 of 10
KARAMSHAHI AND GHORBANI-VAGHEI
TABLE 2 (Continued)
aReaction conditions: benzaldehyde (1 mmol), aniline (1 mmol), dimethyl acetylenedicarboxylate (1 mmol), BF@Propyl/dopamine/Pd (0.06 g), EtOH (5 ml),
reflux.
SCHEME 3 Proposed mechanism for formation of furans

EFFICIENT SYNTHESIS OF MULTIPLY SUBSTITUTED FURANS
7 of 10
(ppm) 3.57 (s, 3H, OCH3), 3.67 (s, 3H, OCH3), 6.69 (s, 1H,
CH), 6.89 (m, 2H, Ar-H), 7.22 (m, 2H, Ar-H), 7.34 (m,
2H, Ar-H), 7.43 (m, 1H, Ar-H), 11.91 (s, 1H, NH); 13C
NMR (100 MHz, CDCl3): δH (ppm) 51.1, 55.1, 57.9, 107.5,
114.0, 124.1, 128.7, 128.9, 129.6, 130.5, 133.6, 137.5, 155.0,
157.1, 162.4, 164.3; MS (m/z): 407.0 (M+), 375.0, 340.0,
312.0, 279.0, 244.1, 198.0, 149.1 (100%), 122.1, 83.0, 47.0.
3 | RESULT AND DISCUSSION
In continuing our work on the use of catalysts,[32–37]
herein, we focus on further improvement of the catalytic
efficiency and the development of new catalyst with high
activity. Therefore, this promising procedure was investi-
gated for the synthesis of furans.
FIGURE 1 FT-IR spectra: a) BF; b) BF@Propyl; c)
BF@Propyl/dopamine; d) BF@Propyl/dopamine/Pd 97x67mm
(300 x 300 DPI)
Firstly, we raised the reaction effectiveness by using
BF@Propyl/dopamine/Pd as a catalyst in different sol-
vents (Table 1, entries 1–4). Therefore, ethanol showed to
be the best solvent that afforded the product in 82% yield
(Table 1, entry 4). Then, we studied the influence of cata-
lyst loading on the model reaction (Table 1, entries 4–7).
The results revealed that a rise in catalyst loading (0.06 g)
increases the yield of the product (Table 1, entry 5).
Meanwhile, in the case of increasing the catalyst loading
to 0.1 g, noticeable change was not detected in the prod-
uct yield (Table 1, entry 6). On the other hand, a reduc-
tion in catalyst loading (0.025 g) reduces the product
yield to 45% (Table 1, entry 7). Accordingly, a catalyst
loading of 0.06 g of BF@Propyl/dopamine/Pd catalyst in
ethanol at reflux condition for 65 min was the best reac-
tion conditions for the synthesis of 5-oxo-2-phenyl-
4-(phenylamino)-2,5-dihydrofuran-3-carboxylate
2.8.10 | Methyl 4-((4-methoxyphenyl)
amino)-2-(2-nitrophenyl)-5-oxo-
2,5-dihydrofuran-3-carboxylate 4j
White solid; M.p. 204–207 ꢀC; FT-IR (KBr): υ¯ (cm−1):
3428, 3189, 2955, 1712, 1676, 1534, 1514, 1460, 1386,
1
1255, 1183, 1031; H NMR (400 MHz, CDCl3): δH (ppm)
3.51 (s, 3H, OCH3), 3.67 (s, 3H, OCH3), 6.74 (s, 1H, CH),
6.90 (m, 2H, Ar-H), 7.29 (m, 1H, Ar-H), 7.53 (m, 4H, Ar-
H), 7.86 (m, 1H, Ar-H), 12.11 (s, 1H, NH); 13C NMR
(100 MHz, CDCl3): δC (ppm) 51.2, 54.7, 55.1, 111.0, 114.0,
124.1, 124.6, 127.4, 128.9, 129.2, 130.9, 133.6, 150.2, 153.5,
157.0, 162.2, 164.1; MS (m/z): 384.1 (M+), 352.1, 327.1,
300.1, 263.1, 235.1, 207.1, 175.0, 149.1 (100%), 122.1, 77.1,
51.1.
(4a) (Table 1, entry 5).
2.8.11 | Methyl 2-(2,4-dichlorophenyl)-
4-((4-methoxyphenyl)amino)-5-oxo-
2,5-dihydrofuran-3-carboxylate 4 k
Regarding the optimized reaction conditions, we
investigated these conditions for aromatic aldehydes
and amines bearing either electron-withdrawing or
electron-donating substituents and aromatic amines with
dimethyl acetylenedicarboxylate (Scheme 1). The cases
in Table 2 obvious that the catalysis progressed well for
White solid; M.p. 230–235 ꢀC; FT-IR (KBr): υ¯ (cm−1):
3327, 2954, 2834, 1720, 1686, 1655, 1512, 1434, 1374,
1
1314, 1247, 1125, 1038; H NMR (400 MHz, CDCl3): δH
a wider variety of aryl aldehydes and aromatic
FIGURE 2 EDX spectrum: a) BF; b) BF@Propyl/dopamine/Pd

8 of 10
KARAMSHAHI AND GHORBANI-VAGHEI
amines, given that the corresponding furan to be in high
yields.
We have suggested a plausible mechanism for the
synthesis of furan derivatives in the presence of
BF@Propyl/dopamine/Pd as a green catalyst (Scheme 3).
Primary, dimethyl acetylenedicarboxylate, which is
activated by palladium (intermediate I), is attacked by
amines and intermediate II is formed. Subsequently,
aldehyde and intermediate II reacted together and
resulted in the intermediate III, then the intramolecular
ringing reaction occurred with the oxygen attack to the
carbonyl group and the exit of the OMe molecule and
finally the product formed.
TABLE 3 Atomic compositions of BF and
BF@Propyl/dopamine/Pd particles determined by EDX
The results of the IR spectrum of the catalyst
(BF@Propyl/dopamine/Pd) are shown in Figure 1. From
the spectrum of BF (a), the characteristic peaks of O-H at
about 3000–3650 cm−1 were observed, and the absorption
peak at about 1120 cm−1 was connected with Si-O-Si
groups. The spectrum (b) corresponds to BF@(CH2)3-Cl.
The peak in the region 2959 cm−1 is related to the methy-
lene groups, which represented the successful reaction of
(3-chloropropyl)triethoxysilane with a basalt fiber sub-
strate. In spectrum c, N-H peaks appear in the region of
Samples/
Elements
BF@Propyl/
dopamine/Pd (%)
BF (Atomic%)
C
16.3
23.3
12.6
4.8
1.9
O
22.6
trace
trace
trace
trace
24
Fe
Ti
Al
Ca
Si
7.4
9.4
26.2
-
3350 cm−1
,
besides, wide absorption peak at
Pd
51.5
1350–2750 cm−1 is related to the -OH groups. Another
absorption band at 1344 cm−1 and 1358 cm−1 are related
to the C-N and C-O groups of dopamine, respectively,
and indicate a successful reaction of dopamine with
BF@(CH2)3-Cl.
The decrease in peak intensity (d) in the 3350 cm−1
region denoted that the BF@Propyl/dopamine/Pd coat-
ing had been successfully appended onto the BF surface.
Figure 2 (a,b) is a spectrum of EDX basalt fiber
(BF) and catalyst (BF@Propyl/dopamine/Pd). Figure 2
(a) shows the presence of O, C, Fe, Ca, Al, Ti and Si ele-
ments on the basalt fiber substrate. Also, in Table 3
exhibits a composition of 26.2 atomic% Si, 9.4% Ca, 4.8%
Ti, 12.6% Fe, and 7.4% Al, which confirmed that the
basalt fibers contains diverse metal oxides.
The EDX peaks in Figure 2(b) confirms that the
positioning of the palladium particles on the basalt
fiber substrate. The EDX is only a surface analytical
FIGURE 3 XRD patterns: a) BF; b) BF@Propyl/dopamine/Pd
FIGURE 4 Morphology and particle size: a) BF; b) BF@Propyl/dopamine/Pd

EFFICIENT SYNTHESIS OF MULTIPLY SUBSTITUTED FURANS
9 of 10
procedure and, hence, the relative concentrations of the
components may vary depending on the position of the
surface.
Figure 3 presents the XRD patterns of the catalyst
(BF@Propyl/dopamine/Pd). The corresponding XRD
spectra have been investigated in the range of 2θ
between 5–80 ꢀC. The peaks at 2θ values of 40.0, 46.6 and
68.4 were related to palladium particles on the BF
substrate.
Scanning electron microscopy (SEM) was used to
obtain information on the surface morphology of the
basalt fiber and the catalyst synthesized. In the SEM
images of Figure 4(a), the basalt fiber shows plate shape.
The observed tiny particles on the BF substrate show the
presence of palladium particles (Figure 4(b)).
range of 470–600 ꢀC. According to these results, the
catalyst was stable to a very high-temperature range and
has been shown to be attributed to the strong interaction
of dopamine with the basalt fiber surface, which
prevents the catalyst from decomposing rapidly at low
temperatures.
In this respect, the recovery and reusability of
BF@Propyl/dopamine/Pd were inquired into the reaction
of benzaldehyde (1.0 mmol), aniline (1.0 mmol), ace-
tylenedicarboxylate (1.0 mmol) in EtOH under reflux
conditions using 0.06 g of the catalyst. At the end of the
experiment, BF@Propyl/dopamine/Pd was readily sepa-
rated from the reaction mixture using a filter, washed
several times with warm deionized water and acetone
and dried at 100 ꢀC. Then, the recovered catalyst was
reused for a subsequent fresh batch of the reaction under
similar conditions.
Thermal weight analysis (TGA) was performed to
illustrate the thermal stability of the BF@Propyl/dopa-
mine/Pd catalyst (Figure 5). The first weight loss occurs
The BF@Propyl/dopamine/Pd can be reused up to
the fifth cycle with a minor decrease in yield indicating
its catalytic efficiency (see Figure 6).
ꢀ
at temperatures below 100 C, which may be related to
the residual water and solvents used during catalyst syn-
thesis. Subsequent weight loss was related to palladium
removal and occurred in the temperature range of
ꢀ
100–145 C. Propyl groups attached to the surface of the
4 | CONCLUSION
basalt fiber also decomposed in the temperature range of
150–100 ꢀC. The temperature drops in the range of
Basalt fiber can be considered as eco-friendly and non-
hazardous materials. It is not a new material, but its
applications are surely innovative in many industrial and
economic fields, because of its good mechanical, chemi-
cal and thermal performances.
ꢀ
450–350 C is also related to dopamine. Finally, the last
layer (basalt fiber) was decomposed in the temperature
Basalt fiber as an eco-friendly catalyst has resulted in
good to excellent yields of desired furan products.
ACKNOWLEDGMENTS
The authors wish to thank Bu-Ali Sina University, Center
of Excellence Developmental of Environmentally
Friendly Methods for Chemical Synthesis (CEDEFMCS).
ORCID
Zahra Karamshahi https://orcid.org/0000-0003-2777-
6629
FIGURE 5 TGA curve of BF@Propyl/dopamine/Pd
Ramin Ghorbani-Vaghei https://orcid.org/0000-0001-
8322-6299
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SUPPORTING INFORMATION
Additional supporting information may be found online
in the Supporting Information section at the end of this
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