Zeolite ZSM-11 as a reusable and efficient catalyst promoted improved protocol for synthesis of 2,4,5-triarylimidazole derivatives under solvent-free condition

Article abstract of DOI:10.1007/s11164-021-04423-9

Zeolite ZSM-11 catalyst was prepared by hydrothermal method and characterized by FTIR, XRD, SEM, HRTEM, EDS, and BET analysis techniques. The catalyst shows good catalytic activity toward synthesis of 2,4,5-triarylimidazole derivatives which is prepared b

Full text of DOI:10.1007/s11164-021-04423-9

Research on Chemical Intermediates
https://doi.org/10.1007/s11164-021-04423-9
Zeolite ZSM‑11 as a reusable and efcient catalyst
promoted improved protocol for synthesis
of 2,4,5‑triarylimidazole derivatives under solvent‑free
condition
Sudarshan S. Dipake, et al. [full author details at the end of the article]
Received: 13 December 2020 / Accepted: 27 February 2021
© The Author(s), under exclusive licence to Springer Nature B.V. 2021
Abstract
Zeolite ZSM-11 catalyst was prepared by hydrothermal method and characterized
by FTIR, XRD, SEM, HRTEM, EDS, and BET analysis techniques. The catalyst
shows good catalytic activity toward synthesis of 2,4,5-triarylimidazole derivatives
which is prepared by using benzil, aldehyde and ammonium acetate in solvent-free
condition. The reaction, one pot synthesis is highly adaptable and eco-friendly and
has several merits such as short reaction time, mild reaction conditions, and high
yield. The ease of reusability and recovery of catalyst for fve consecutive reactions
makes this protocol highly suitable.
Graphical abstract
Keywords 2,4,5-triarylimidazole derivatives · Multicomponent reaction · ZSM-11 ·
Zeolite catalyst · Solvent-free reaction
Vol.:(0123456789)
1 3

S. S. Dipake et al.
Introduction
The imidazoles are one of the most important substructures found in natural
products (e.g., histidine, biotin, histamine and pilocarpine alkaloids), agrochemi-
cal (e.g., herbicide, fungicide, plant growth regulators), pharmacologically active
compounds (e.g., analgesic, anti-infammatory, antibacterial, antitumor activities,
anti-thrombotic agents, and therapeutic agents), and many substituted imidazoles
are extensively used as glucagon receptor antagonist, inhibitors of interleukin
(IL)-1, 5-lipoxygenase [1–6]. There are several drug moieties with imidazole core
such as Trifenagrel, Eposartan, Olmesartan, Losartan, P38 kinase inhibitor (SB
203,580), and cyclooxygenase-2 (COX-2) inhibitor II (Fig. 1) [5, 7].
The N-heterocyclic imidazole family has expanded its applications in various
felds such as cosmetics, polymer chemistry, agrochemicals, materials chemistry
(optical electronics, dye sensitized solar cells (OLEDS) [2, 4]. Imidazole deriva-
tives are also used in photography as photosensitive compounds and in industry
as a corrosion inhibitor of defnite transition metals [8].
Generally, synthesis of 2,4,5-trisubstituted imidazole derivatives via three-
component cyclo-condensation of 1,2-diketones, diverse aldehyde, and ammo-
nium acetate. Recently, several methods have been described for the synthesis
of 2,4,5-triarylimidazole derivatives by using microwave, ionic liquids [9],
InCl3.3H2O [10], AcOH [11] PEG-400 [12], DABCO [13], silicasulfuric acid
[14], ytterbium perfuorooctanesulfonate [15], ytterbium trifoliate [16], H2SO4
[17], Oxalic acid [18], and P-toluene sulfonic acid [19]. Most of these synthetic
methods sufer from one or more consequential drawback such as long duration,
harsh reaction conditions, poor yields, complex workup, prolonged time periods,
occurrence of side reactions leading to mixture of products, hazardous or expen-
sive acid, moisture-sensitive catalysts, excessive reagents or catalyst. Eco-friendly
and efective approach for the synthesis 2,4,5-triarylimidazole derivatives is still
in the demand due to increasing market value of imidazole moieties.
In this sense, ZSM-11 zeolite catalysts have various advantages, like reusa-
bility, environmental acceptability, and easy separation of products. It exhibits
excellent catalytic properties in some reactions such as higher parafn hydro-
isomerization [20], dehydration of glycerol to acrolein, [21] catalytic pyrolysis of
heavy oil aromatization, and isomerization of 1-hexene [22]. ZSM-11 zeolites are
also well-known heterogenous catalysts and have been extensively utilized in the
production of petrochemicals, they have unique structures, high thermal stability,
and shape selectivity [23] to enhance demand in organic transformations. It was
prepared by kokotailo et al. [24, 25] in 1978 with tetrabutyl ammonium (TBA)
as the structure-directing agent (SDA). ZSM-11 is one type of high-silica zeolite
with MEL topology [26].
Herein, in the present work, to overcome all limitations in the synthesis of
2,4,5-triarylimidazole derivatives, we developed safe, efcient, reusable, and eco-
friendly ZSM-11 catalyst. We also describe a sustainable, efcient, cost-efective,
and excellent protocols for the synthesis of 2,4,5-triarylimidazole derivatives
using benzil, diverse aldehyde and ammonium acetate as an ammonia source
1 3

Zeolite ZSM‑11 as a reusable and efcient catalyst promoted…
Fig. 1 Some of the drugs of imidazole moiety and structure of P38 kinase inhibitor- I and COX-2 inhibi-
tor- II
under solvent-free condition in the presence of ZSM-11 catalyst. It observed that
the catalyst shows strong catalytic activity toward synthesis of 2,4,5-triarylimida-
zole derivatives under solvent-free condition.
1 3

S. S. Dipake et al.
Experimental
Chemicals and methods
All the chemicals were purchased by Sigma-Aldrich chemical company with high
purity without further purifcation. Solvents were distilled and purifed by stand-
ard procedure and used in reaction. Several characterization techniques have been
done, using calibrated instruments, including powder X-ray difraction (XRD) using
a Bruker D8-Advanced difractometer using Cu Kα radiation between 5° and 80°
(2θ values). The FTIR spectra (Fourier transform infrared spectra) were revealed
using a Shimadzu FTIR 8300 spectrophotometer, and element composition (EDS)
was recorded on Objects 8724. The specifc surface area and pore volume were cal-
culated on Quantachrome instruments version 3.01 by Brunauer–Emmett–Teller
(BET) method. Morphology of the zeolite samples was characterized by FE-SEM
on Nova Nano SEM NPEP303 and high-resolution transmission electron micros-
copy (HRTEM) images were obtained using a JEOL JEM 2100 Plus microscope.
1
Reactions were indicated by thin-layer chromatography (TLC). The H NMR
(400 MHz) and 13C NMR (101 MHz) were run on a Bruker (400 MHz) spectrom-
eter using tetramethyl silane (TMS) as an internal reference. All reactions were car-
ried out using a laboratory assembly of oil bath with magnetic stirrer. Melting points
were measured in open capillary tube.
Catalyst preparation
Synthesis of ZSM-11 catalyst was prepared by using hydrothermal pathway as
shown in Scheme 1. In frst step, the mixture of 23 ml of TEOS (Tetra ethyl ortho-
silicate) as a silica source, 20 ml of alcohol, and 20 ml of distilled deionized
water were stirred vigorously to form silicate solution. In second step, 1.73 gm of
Al(NO3)3 (aluminum nitrate) as an alumina source was taken in 20 ml of distilled
deionized water and 27 ml of TPAOH (tetrapropyl ammonium hydroxide) as a struc-
ture-directing agent as well as base was added for maintaining pH 12 with vigorous
stirring to form alumina solution. The solution was mixed by dropwise addition with
vigorous stirring, the mixture was then stirred for 30 min, which resulted in trans-
parent viscous gel and was transferred in a Tefon-lined stainless-steel autoclave and
closed tightly for hydrothermal treatment at 175 °C for 48 h. Solid product formed
was washed with distilled water for several times and dried in an oven at 120 °C
for 2 h and fnally the product was calcined at 550 °C for 6 h in a mufe furnace
and then cooled. The catalyst was characterized and then utilized in the synthesis of
2,4,5-triarylimidazole derivatives.
Synthesis of 2,4,5‑triarylimidazole derivative
The suspension of benzil (1 mmol), benzaldehyde (1 mmol), and ammonium
acetate (3 mmol) were stirred in oil bath at 110 °C for 30 min under solvent-free
1 3

Zeolite ZSM‑11 as a reusable and efcient catalyst promoted…
Scheme 1 Schematic representation of synthesized ZSM-11 zeolite by hydrothermal method using
TPAOH as a structure-directing agent.
condition using cold water condenser in presence of ZSM-11 (0.05 gm) as a
catalyst, progress of reaction was monitored by TLC using petroleum ether/ethyl
acetate (6:4) as a solvent system. Completion of reaction was indicated by dis-
appearance of starting materials on the TLC spot. The mixture was cooled, and
5 ml of acetone was added in reaction mixture for the separation of catalyst by
fltration. The catalyst was separated and then activated at 110 °C in oven for
30 min, and crude product was poured on ice cold water. The obtained precipi-
tate was washed and recrystallized in ethanol to ofer pure product. We applied
same procedure for the synthesis of the other derivatives of model reaction,
which is shown in Table 1.
Spectral data of represented compound
2‑(4‑Nitrophenyl)‑4,5‑diphenylimidazole (4e)
Yellow solid; m.p.: 230–232 °C, Lit.14, 232–33 °C, IR (υmax cm−1): 1331 and
1
1508 (NO2), 1591 (C=N), 3383 (NH) cm−1. H NMR (400 MHz, DMSO-d6,
δ
ppm) 13.15 (s, 1H), 8.42 – 8.21 (m, 4H), 7.54 (d, 4H), 7.49–7.20 (m, 6H). 13C
NMR (101 MHz, DMSO-d6, δ ppm) 146.54, 143.39, 136.11, 128.51, 127.18,
125.74, 124.27; HRMS for C21H15N3O2, M+: 342.11.
1 3

S. S. Dipake et al.
Table 1 Synthesis of 2,4,5-triarylimidazole derivatives catalysed by ZSM-11 catalyst
Entry
R
Producta
Yieldb %
Timec (Min.)
M.P Found (°C)
Reportedd (°C)
1
2
3
4
5
6
7
8
9
10
H
4-CH3
4-Cl
3-NO2
4-NO2
4-OCH3
4-OH
3-OH
4-F
4a
4b
4c
4d
4e
4f
4g
4h
4i
90
85
85
80
88
80
81
82
90
78
30
32
34
35
32
40
38
35
30
35
271–273
230–232
260–262
>360
242–243
230–231
256–258
259–260
190–191
258–260
270–272[35]
231–232 [36]
257–260[37]
>360 [38]
241–242 [39]
231–232 [3]
254–256 [2]
260–261 [40]
190 [41]
4-Br
4j
254–256 [42]
Reaction conditions: Model reaction; 1 benzil (1 mmol), 2 aldehyde (1 mmol), and 3 ammonium acetate
(3 mmol) in the presence of ZSM-11 catalyst (0.05 g) at 110 °C, aproduct, bisolated yield, ctime, dmelting
point found, and emelting points reported in the parentheses refer to the literature melting points
2‑(4‑bromophenyl)‑4,5‑diphenyl‑1H‑imidazole (4 k)
White solid; m.p.: 258–260° C, Lit.27 m.p.: 254–256 °C; IR (υmax cm−1): 3023
1
(Ar–H), 1677 (C=N), 1483, 1593 (C=C, Ar), 609 (C–Br). H NMR (400 MHz,
DMSO-d6, δ ppm) 12.81 (s, 1H), 8.06 (d, 2H), 7.68 (d, 2H), 7.55 (dd, 4H), 7.47–7.18
(m, 6H). 13C NMR (101 MHz, DMSO-d6, δ ppm) 144.50, 137.36, 135.02, 131.67,
130.94, 129.56, 128.66, 128.43, 128.20, 127.86, 127.11, 126.60, 121.41; HRMS for
C21H15N2, M+: 375.04.
2‑(4‑methylphenyl)‑4,5‑diphenyl‑1H‑imidazole (4b)
White solid; m.p 231–232 °C, Lit.14 m.p; 230–232 °C IR (υmax cm−1): 3464 (NH),
1
3037 (Ar–H), 1596 (C=N), H NMR (400 MHz, DMSO-d6, δ ppm) 12.60 (s, 1H),
7.97 (d, 2H), 7.54 (d, 2H), 7.50 (d, 2H), 7.44 (d, 2H), 7.37 (d, 1H), 7.30 (d, 4H),
7.21 (d, 1H), 2.35 (s, 3H). 13C NMR (101 MHz, DMSO-d6, δ ppm) 145.65, 137.68,
136.91, 135.25, 131.15, 129.25, 128.64, 128.41, 128.17, 127.93, 127.68, 127.05,
126.46, 125.16, 20.89; HRMS for C22H18N2, M+: 311.15.
4‑(4,5‑diphenyl‑1H‑imidazol‑2‑yl) phenol (4 g)
Orange solid; m.p. 256–258 °C, Lit. 2, 254–256 °C IR (υmax cm−1): 3461 (NH),
1
3033 (Ar–H) 1603 (C=N). H NMR (400 MHz, DMSO-d6, δ ppm) 12.49 (s, 1H,
1 3

Zeolite ZSM‑11 as a reusable and efcient catalyst promoted…
NH), 9.79 (s, 1H, OH), 7.95 (d, 2H), 7.54 (d, 4H), 7.42–7.22 (m, 6H, Ar–H), 6.90
(d, 2H). 13C NMR (101 MHz, DMSO-d6, δ ppm) 157.87, 146.17, 128.43, 127.72,
126.95, 121.71, 115.50; HRMS for C21H16N2O, M+: 313.13.
2‑(4‑fuorophenyl)‑4,5‑diphenyl‑1H‑imidazole (4j)
White solid; m.p. 190–191 °C, Lit. 14, 188–190 °C IR (υmax cm−1): 3050 (Ar–H),
1
1603 (C=N), 1540 (C=C). H NMR (400 MHz, DMSO-d6, δ ppm) 12.72 (s, 1H),
8.14 (dd, 2H), 7.54 (dd, 4H), 7.44 (d, 2H), 7.34 (m, 5H, Ar–H), 7.25–7.20 (d, 1H).
13C NMR (101 MHz, DMSO-d6, δ ppm) 163.35, 160.91, 144.71, 137.08, 135.12,
131.05, 128.67, 128.41, 128.26, 128.19, 127.79, 127.37, 127.29, 127.07, 127.02,
126.54; HRMS for C21H15 FN2, M+: 315.12.
5‑triphenyl‑1H‑imidazole (4a)
White solid; m.p.: 271–273 °C, Lit.28 m.p.: 270–272 °C; IR (υmax cm−1): 3034
(Ar–H), 1587 (C=N), 1444, 1587 (C=C aromatic). 1H NMR (400 MHz, CHLORO-
FORM-D/ DMSO-D6, δ ppm) 8.33–7.87 (d, 2H), 7.52 (d, 4H), 7.36 (dd, 2H), 7.26
(m, 5H, Ar–H), 7.20 (d, 2H). 13C NMR (101 MHz, CHLOROFORM-D/ DMSO-
D6, δ ppm) 146.37, 130.49, 128.58, 128.37, 128.27, 128.14, 127.08, 127.05, 125.63;
HRMS for C21H16N2, M+: 297.14.
Result and discussion
Characterization of catalyst
Synthesis of ZSM-11 catalyst by hydrothermal method was done and then after that
the calcination was carried out at 550 °C. The weight of catalyst decreased from the
actual weight, due to the loss of surfactant and moisture. Fourier transform infrared
spectroscopy (FTIR), X-ray powder difraction (XRD), scanning electron micros-
copy (FESEM), Brunauer–Emmett–Teller (BET) method, energy-dispersive spec-
trometry (EDS), and high-resolution transmission electron microscopy (HRTEM) of
samples were collected to investigate the efect of morphology on the framework of
product zeolites. As shown in Fig. 2a, the samples revealed characteristic absorption
bands of ZSM-11 catalyst at 445, 547, 800, 1066 and 1250 cm−1. The absorption
bands at 1250, 1066, 1022 and 800 cm−1 could be assigned to the external asymmet-
ric, internal asymmetric, silanol group [O3Si–OH], and external symmetric stretch-
ing of Si–O–T linkage in ZSM-11 framework, respectively. The bending vibration
of TO4 (T=Si or Al) in ZSM-11 framework was recorded at around 445 cm−1,
while the vibration band at around 547 cm−1 indicated the presence of the double
fve rings of the characteristic structure of pentasil family zeolite (MEL) [27]. Par-
ticularly, due to broad peak from 900 to 1300 the weak absorption band related to
[O3Si–OH] units and external asymmetric stretching of Si–O–T linkage showed
no defned absorption but showed on intense neighboring band at 1066 cm−1. It
was postulated that the close stack of nanocrystals resulted in the disappearance
1 3

S. S. Dipake et al.
Fig. 2 FTIR of ZSM-11 (a), XRD of ZSM-11 (b)
of surface [O3Si–OH] units and particle size of zeolites decreased to some extent
(Fig. 2a) [22]. It is interesting that ZSM-11 type zeolite shows intense band at near
550 cm−1 whose position changes with aluminum content. Nevertheless, the absence
of the FTIR band around 550 cm−1 defnitely indicates that ZSM-11 framework type
zeolite is not present in the sample [22, 28].
Crystallinity of catalyst is conformed by X-ray difraction analysis using Cu
Kα radiation (λ = 1.5406 A°). Generally, it is very difcult to prepare pure-phase
1 3

Zeolite ZSM‑11 as a reusable and efcient catalyst promoted…
ZSM-11 without any ZSM-5 phase because of the similarities in topology
between both types of zeolites. The appearance of doublet peaks in the range
between 23° and 25° and a single refection peak at 2θ of 45.4° demonstrated the
absence of ZSM-5 intergrowth in ZSM-11 particles [22, 27]. International zeolite
association data also confrm the synthesized zeolite sample near to the ZSM-11
zeolite type and MEL topology in which the highest intensity double peak was
observed in between 2θ° value 23° to 25° and one single peak observed at 45.4°
are used to distinguish MEL from that of the MFI topology [29]. The intense
peak at 23.30° is near about ZSM-11-type phase with MEL topology [30]. which
is shown in Fig. 1b. Peak shows at 2θ° 8.06, 9.01, 14.95, 23.30, 24.01, 45.4 with
corresponding plane (100), (011), (112), (221), (031), (522) respectively, which
confrm the ordered orthorhombic framework and having ZSM-11 type phase
with MEL topology. There is slightly diferences observed in the 2θ° value of
reported ZSM-11 due to alkyl chains of TPAOH which give rise to an slightly dif-
ferent zeolitic framework [31].
Scanning electron microscopy (FESEM) of material was used to determine sur-
face morphology and crystal size with diferent magnifcation and micrograph,
which is presented in Fig. 5a and b. FESEM image suggest that aluminum is
agglomerated in silicate framework which has irregular sheet type shape. Structure
and morphology of catalyst determined by high-resolution transmission electron
microscopy (HRTEM) show that most of the particles are irregular spherical and
their diameters vary between 5 and 20 nm. Figure 5c reveals that these particles
were constructed by many primary nanocrystals of 5–10 nm. HRTEM micrographs
and microdifraction have shown that each grain of sample 100 nm has formed by
the aggregation of very small zeolite particles (5–10 nm) [28]. It can also be seen
that some mesopores appear on the surface and edge of ZSM-11 crystals. The typi-
cal cofn-shape morphology of the ZSM-11 zeolite observed [32]. Figure 5d show
that the lattice fringes of several adjacent nanorods in the particles were completely
parallel in the same direction but some particles were in slightly diferent direc-
tion, demonstrating their highly oriented and ordered intergrowth structure. The
interfringe distances of the representative ZSM-11 nanorods were measured to be
between 1 and 2 nm. The crystal morphology shown in HRTEM of 10 and 20 nm
are nearly similar to the FESEM images of several parallel single-crystalline-like
matrices [31]. We know the elemental composition of material from EDX analy-
sis. Figure 3 shows material having oxygen 49.17%, silicon 46.65%, and aluminum
4.18% and EDX composition elemental mapping of ZSM-11 material shown in
Fig. 6. The catalyst was characterized by using BET and BJH methods. Pore size
distribution was analyzed by using N2 adsorption–desorption measurement. Total
surface area, pore volume, and pore radius observed were 369.791 m2/g, 7.625e-
01 cc/g, and 4.12377e+01 Å, respectively. Furthermore, the micropore and external
surface area of catalyst were 288.388 and 349.937 m2/g, respectively. According to
the IUPAC classifcation N2 adsorption–desorption isotherms of the ZSM-11 zeo-
lites, Fig. 4 are type IV in nature with H1-type hysteresis loop [33]. The nitrogen
adsorption isotherm shows a steep regular increase at a low relative pressure and a
hysteresis loop from P/P0 =0.45 to about P/P0 =1 which demonstrate the coexist-
ence of micropores and intercrystal mesopores [22, 32, 34] (Figs. 5, 6).
1 3

S. S. Dipake et al.
Fig. 3 EDX report of ZSM-11 Catalyst
Fig. 4 Nitrogen adsorption–desorption isotherms of ZSM-11
Optimization of catalyst
Model reaction are monitored at various temperature, amount of catalyst and sol-
vent at 110 °C under solvent-free condition, which shown in Table 2. We have
1 3

Zeolite ZSM‑11 as a reusable and efcient catalyst promoted…
Fig. 5 a and b FE-SEM image of ZSM-11, c and d HR-TEM image of ZSM-11
compared our results with results of some other solvent for the synthesis of 2,4,5
triaryl imidazole and concluded that the solvent like water, ethanol, chloroform,
and DMF did not give better yield as compared to the solvent-free condition of
model reaction. Again, we checked the catalytic activity with diverse temperature
and found that best results are obtained at 110 °C in solvent-free condition, fur-
ther increase in temperature up to 120 °C did not show any improvement in prod-
uct yield. The model reaction did not proceed in the absence of catalyst even after
240 min, which was shown in Table 2. Also, we optimized the actual amount
of catalyst that gives better yield. According to Table 2, as amount of catalyst
increased, the percentage of 2,4,5-triarylimidazole derivatives also increased
due to the presence of more active sites on the catalyst, and it was found that
0.05 gm catalyst gave better yield within short reaction time in solvent-free con-
dition. There were no further increased in yield after increasing amount of cata-
lyst (0.05 gm). We used diferent aldehyde as a substrate for this model reaction
in presence of ZSM-11 catalyst under solvent-free condition, and the results are
1 3

S. S. Dipake et al.
Fig. 6 EDX, elemental composition mapping of ZSM-11 (a), O (b), Al (c), and Si (d)
Table 2 Condensation of benzil, benzaldehyde, and ammonium acetate under diferent reaction condi-
tions
Entry
Solvent
Catalyst amount Condition (°C)
(gm)
Time (Min.)
Yielda (%)
1
2
3
4
5
6
7
8
9
10
11
12
13
Solvent-free
Solvent-free
Solvent-free
Solvent-free
Solvent-free
Solvent-free
Solvent-free
Solvent-free
Solvent-free
H2O
None
0.01
0.02
0.03
0.04
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
110
110
110
110
110
110
80
100
120
80
240
240
180
120
60
30
120
60
NR
10
35
55
80
90
40
60
90
10
35
50
55
30
120
120
120
120
EtOH
Chloroform
DMF
80
80
80
Reaction conditions: benzil: benzaldehyde: ammonium acetate (1:1:3 mmol ratio), Yielda refer to the iso-
lated pure product
1 3

Zeolite ZSM‑11 as a reusable and efcient catalyst promoted…
summarized in Table 1. ZSM-11 catalyst is more efective for the wide variety
of aldehyde with corresponding imidazole derivative with excellent yield, easy
workup, and short reaction time.
Again, we have compared our catalyst to other reported catalyst such as ace-
tic acid, Montmorillonite K10, Polymer-ZnCl2, Nano-SnCl4-SiO2, CAN and
Yb (OTf)3 in the 2,4,5-triarylimidazole derivatives, which is shown in Table 3.
Therefore, after optimization of reaction condition, we clearly demonstrate that
the solvent-free synthesis of 2,4,5-triarylimidazole derivatives in presence of
ZSM-11 (0.05 gm) catalyst at 110 °C was a best reaction condition.
A mechanism of catalytic activity of ZSM-11 catalyst in synthesis of 2,4,5-tri-
arylimidazole derivatives is shown in Scheme 2. Carboxyl groups of benzil and
aldehydes (1) are activated by ZSM-11 catalyst. Then nucleophilic attack of the
nitrogen of ammonia, which was formed from ammonium acetate, on the acti-
vated carbonyl group of benzil and aldehydes resulted in the formation of α-imino
ketone intermediate (3) and aryl aldimine intermediate (4), then followed by the
nucleophilic attack of aryl aldimine intermediate (4) to the carbonyl carbon of
α-imino ketone (3), give up the intermediate (5). After the cyclization, formation
of intermediate (6) turns to 2,4,5-triarylimidazole derivatives by dehydration.
Catalyst activation and reusability
Solid ZSM-11 catalyst is insoluble in most of the solvent, so it can be easily sepa-
rate out from reaction mixture by fltration with the help of suction pump, recov-
ered catalyst washed with acetone or any other polar solvent for 2–3 times. For
activation, transfer washed recovered catalyst under vacuum-oven for 30 min at
110 °C and recovered catalyst was used for fve runs without any further treat-
ment in subsequent reaction and it was found that catalyst almost have consistent
activity. No observation of any appreciable loss in catalytic activity (Fig. 7).
Table 3 Synthesis of 2,4,5-triarylimidazole derivatives using various reported catalysts
Entry
Catalyst
Time (min)a
Yield (%)b
Referencec
1
2
3
4
5
7
8
9
Without catalyst
CH3COOH
180
120
90
240
120
360
160
30
NR
40
70
96
97
75
92
90
–
[43]
[42]
[44]
[45]
[7]
[16]
Present work
Montmorillonite K10
Polymer–ZnCl2
.
Nano-SnCl4 SiO2
CAN
Yb(OTf)3
ZSM-11
a
Reaction conditions: benzil/benzaldehyde/ammonium acetate (1:1:3 mmol ratio), time, bisolated yield,
creference
1 3

S. S. Dipake et al.
Scheme 2 Possible mechanism of synthesis of 2,4,5-triarylimidazole derivative using ZSM-11 zeolite as
a catalyst
Conclusion
In this work, we have successfully synthesized ZSM-11 catalyst and developed
easy and efcient three-component method to prepare a variety of 2,4,5-triarylim-
idazole derivatives in the presence of ZSM-11 catalyst in solvent-free condition.
We have demonstrated that the ZSM-11 is a potential alternative to the use of
other catalyst for efcient synthesis of wide range of 2,4,5-triarylimidazole deriv-
atives. This procedure has many obvious advantages compared to those reported
in the previous studies, including the avoidance of discharging harmful catalysts,
low reaction temperature, high yield of products, simplicity of the methodology,
recovery, and reusability of ZSM-11 catalyst for fve consecutive runs. The nota-
ble merits ofered by this methodology are mild reaction conditions, easy workup,
clean reaction profles, good agreement with the clean protocols, and being sol-
vent-free, and this renders the approach as an interesting alternative to existing
methods. Furthermore, products were isolated in excellent yield which signifcant
regarding environmentally benign processes.
1 3

Zeolite ZSM‑11 as a reusable and efcient catalyst promoted…
Synthesis of 2,4,5 Triarylimidazole
100
95
90
85
80
75
70
65
60
55
50
45
40
35
30
25
20
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Fig. 7 Catalyst recycling studies of ZSM-11 catalyst
Supplementary Information The online version contains supplementary material available at https://doi.
org/10.1007/s11164-021-04423-9.
Acknowledgements One of the authors, Mr. Sudarshan S. Dipake, gratefully thankful to the Council of
Scientifc and Industrial Research (CSIR), New Delhi for the award of fellowship and to the Department
of Chemistry, Dr. Babasaheb Ambedkar Marathwada University, Aurangabad-431004 (M.S.), India. for
support and providing the necessary laboratory facility.
Author contributions SSD-Conduct the whole experiment, Writing original draft. MKL-Review and
editing. ASR-Review and editing. STG-Principal author.
Declarations
Confict of interest No potential confict of interest was reported by the authors.
Consent to participate All Authors are agreed for submission.
Consent for publication Agreed to submission.
Data availability Manuscript including all data correct and unpublished.
References
1. S. Dehghan Khalili, S.H. Banitaba, J. Safari, Sci. Iran. 20, 1855 (2013)
2. M. Esmaeilpour, J. Javidi, M. Zandi, New J. Chem. 39, 3388 (2015)
1 3

S. S. Dipake et al.
3. H. Naeimi, D. Aghaseyedkarimi, New J. Chem. 39, 9415 (2015)
4. J. Jayram, V. Jeena, Green Chem. 19, 5841 (2017)
5. A. Shaabani, R. Afshari, S.E. Hooshmand, New J. Chem. 41, 8469 (2017)
6. Y. Chen, R. Wang, F. Ba, J. Hou, A. Ding, M. Zhou, H. Guo, J. Saudi Chem. Soc. 21, 76 (2017)
7. A. Shaabani, A. Maleki, M. Behnam, Synth. Commun. 39, 102 (2009)
8. J. Jayram, V. Jeena, RSC Adv. 8, 37557 (2018)
9. S.A. Siddiqui, U.C. Narkhede, S.S. Palimkar, T. Daniel, R.J. Lahoti, K.V. Srinivasan, Tetrahedron
61, 3539 (2005)
10. J. Wang, R. Mason, D. VanDerveer, K. Feng, X.R. Bu, J. Org. Chem. 68, 5415 (2003)
11. S. Sarshar, D. Siev, A.M.M. Mjalli, Tetrahedron Lett. 37, 835 (1996)
12. X.C. Wang, H.P. Gong, Z.J. Quan, L. Li, H.L. Ye, Chinese Chem. Lett. 20, 44 (2009)
13. S.N. Murthy, B. Madhav, Y.V.D. Nageswar, Tetrahedron Lett. 51, 5252 (2010)
14. A. Shaabani, A. Rahmati, J. Mol. Catal. A Chem. 249, 246 (2006)
15. M.G. Shen, C. Cai, W. Bin Yi, J. Fluor. Chem. 129, 541 (2008)
16. L.M. Wang, Y.H. Wang, H. Tian, Y.F. Yao, J.H. Shao, B. Liu, J. Fluor. Chem. 127, 1570 (2006)
17. H. Weinmann, M. Harre, K. Koenig, E. Merten, U. Tilstam, Tetrahedron Lett. 43, 593 (2002)
18. N.D. Kokare, J.N. Sangshetti, D.B. Shinde, Synthesis (Stuttg). (2007). https://doi.org/10.
1055/s-2007-983872
19. M.M. Khodaei, K. Bahrami, I. Kavianinia, J. Chinese Chem. Soc. 54, 829 (2007)
20. T.L.M. Maesen, M. Schenk, T.J.H. Vlugt, B. Smit, J. Catal. 203, 281 (2001)
21. Y. Gu, N. Cui, Q. Yu, C. Li, Q. Cui, Appl. Catal. A Gen. 429–430, 9 (2012)
22. Q. Yu, C. Cui, Q. Zhang, J. Chen, Y. Li, J. Sun, C. Li, Q. Cui, C. Yang, H. Shan, J. Energy Chem.
22, 761 (2013)
23. L. Zhang, H. Liu, X. Li, S. Xie, Y. Wang, W. Xin, S. Liu, L. Xu, Fuel Process. Technol. 91, 449
(2010)
24. P.M. Piccione, M.E. Davis, Microporous Mesoporous Mater. 49, 163 (2001)
25. G.T. Kokotailo, P. Chu, S.L. Lawton, W.M. Meier, Comptes Rendus Chimie 275, 119 (1978)
26. X. Wang, F. Meng, H. Chen, F. Gao, Y. Wang, X. Han, C. Fan, C. Sun, S. Wang, L. Wang, Comptes
Rendus Chim. 20, 1083 (2017)
27. K.P. Dey, S. Ghosh, M.K. Naskar, Ceram. Int. 39, 2153 (2013)
28. G. Coudurier, C. Naccache, J.C. Vedrine, J. Chem. Soc. Chem. Commun. (1982). https://doi.org/10.
1039/c39820001413
29. W. Song, Z. Liu, L. Liu, A.L. Skov, N. Song, G. Xiong, K. Zhu, X. Zhou, RSC Adv. 5, 31195 (2015)
30. M.M.J. Treacy, J.B. Higgins (eds.), Collection of Simulated XRD Powder Patterns for Zeolites, 5th
edn. (Amsterdam, Elsevier, 2007), p. 477. https://doi.org/10.1016/B978-0-444-53067-7.X5470-7
31. K. Shen, N. Wang, X. Chen, Z. Chen, Y. Li, J. Chen, W. Qian, F. Wei, Catal. Sci. Technol. 7, 5143
(2017)
32. J. Yang, S. Yu, H. Hu, Y. Zhang, J. Lu, J. Wang, D. Yin, Chem. Eng. J. 166, 1083 (2011)
33. S. S. Lapari, Z. Ramli, S. Triwahyono, 2015 (2015).
34. H. Chen, X. Zhang, J. Zhang, Q. Wang, RSC Adv. 7, 46109 (2017)
35. M. Kidwai, P. Mothsra, V. Bansal, R. Goyal, Monatshefte fur Chemie 137, 1189 (2006)
36. S. Balalaie, A. Arabanian, M.S. Hashtroudi, Monatshefte fur Chemie 131, 945 (2000)
37. H.D. Hanoon, S.M. Radhi, S.K. Abbas, A.I.P. Conf, Proc. 2144, 1 (2019)
38. V.S.V. Satyanarayana, A. Sivakumar, Chem. Pap. 65, 519 (2011)
39. A.A. Marzouk, V.M. Abbasov, A.H. Talybov, S.K. Mohamed, World. J. Org. Chem. 1, 6 (2013)
40. J. Safari, Z. Zarnegar, Ultrason. Sonochem. 20, 740 (2013)
41. G.V.M. Sharma, Y. Jyothi, P.S. Lakshmi, Synth. Commun. 36, 2991 (2006)
42. A. Teimouri, A.N. Chermahini, J. Mol. Catal. A Chem. 346, 39 (2011)
43. H.D. Hanoon, E. Kowsari, M. Abdouss, M.H. Ghasemi, H. Zandi, Res. Chem. Intermed. 43, 4023
(2017)
44. L. Wang, C. Cai, Monatshefte fur Chemie 140, 541 (2009)
45. B.F. Mirjalili, A. Bamoniri, M.A. Mirhoseini, Sci. Iran. 20, 587 (2013)
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Zeolite ZSM‑11 as a reusable and efcient catalyst promoted…
Authors and Afliations
Sudarshan S. Dipake1 · Machhindra K. Lande1 · Anjali S. Rajbhoj1 ·
Suresh T. Gaikwad1
*
Suresh T. Gaikwad
gaikwadsuresh12@gmail.com
1
Department of Chemistry, Dr. Babasaheb Ambedkar Marathwada University, Aurangabad,
Maharashtra 431004, India
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