catalysts

Article
Chitosan Capped Copper Oxide Nanocomposite: Efficient,
Recyclable, Heterogeneous Base Catalyst for Synthesis
of Nitroolefins
Mohamed A. El-Atawy 1,2 , Khaled D. Khalil 2,3, * and Ali H. Bashal 2

1 Department of Chemistry, Faculty of Science, Alexandria University, Alexandria 21321, Egypt

2 Department of Chemistry, Faculty of Science, Taibah University, Al-Madinah Almunawarah,
Yanbu 46423, Saudi Arabia
3 Department of Chemistry, Faculty of Science, Cairo University, Giza 12613, Egypt
* Correspondence: [email protected]

Abstract: In this article, chitosan copper oxide nanocomposite was synthesized by the solution casting
method under microwave irradiation. The nanocomposite solution was microwave irradiated at
300 watt for 3 min under optimal irradiation conditions. By suppressing particle agglomeration,
the chitosan matrix was successfully used as a metal oxide stabilizer. The goal of this research
was to create, characterize, and test the catalytic potency of these hybrid nanocomposites in a
number of well-known organic processes. The prepared CS-CuO nanocomposites were analyzed
by different techniques, including Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction
(XRD), and field emission scanning electron microscopy (FESEM). Moreover, energy-dispersive X-ray
spectroscopy (EDS) was used to measure the copper content in the prepared nanocomposite film. The
finger-print peaks in the FTIR spectrum at around 632–502 cm−1 confirmed the existence of the CuO
phase. The CS-CuO nanocomposite has been shown to be an efficient base promoter for nitroolefin
synthesis via the nitroaldol reaction (Henry reaction) in high yields. The reaction variables were
studied to improve the catalytic approach. Higher reaction yields, shorter reaction times, and milder
Citation: El-Atawy, M.A.; Khalil,
K.D.; Bashal, A.H. Chitosan Capped
reaction conditions are all advantages of the technique, as is the catalyst’s reusability for several uses.
Copper Oxide Nanocomposite:
Efficient, Recyclable, Heterogeneous Keywords: chitosan; copper oxide nanoparticles; heterogeneous catalysis; Nitroolefins
Base Catalyst for Synthesis of
Nitroolefins. Catalysts 2022, 12, 964.
https://doi.org/10.3390/catal12090964
1. Introduction
Academic Editor: Victorio Cadierno
Due to their unique features and vast range of applications as potent catalytic agents
Received: 3 August 2022 in various organic transformations, nano catalysis has attracted the interest of many re-
Accepted: 26 August 2022
searchers [1–3]. Nano catalysts have emerged as a low-cost, long-term alternative to
Published: 29 August 2022
hazardous commercial catalysts since they contain nanosized particles with a large, ex-
Publisher’s Note: MDPI stays neutral posed surface area, which increases catalytic activity and regioselectivity in a variety of
with regard to jurisdictional claims in chemical processes [4–19].
published maps and institutional affil- For the above-mentioned reasons, and because of their vast range of applications in
iations. numerous disciplines, many efforts have been made to synthesize new hybrid materials,
including metal oxide nanoparticles. In particular, these hybrid nanocomposites confer a
considerable synergistic effect, as compared to their constituents, that increases their potential
use in many applications, especially in the field of heterogenous catalysis [14–21]. Solid
Copyright: © 2022 by the authors.
catalysts have unique characteristics such as a large surface area, a high atom economy, and
Licensee MDPI, Basel, Switzerland.
the ability to be easily removed from the product, recovered, and reused multiple times
This article is an open access article
without losing catalytic activity. Chitosan, a natural bio-stabilizer, has recently been em-
distributed under the terms and
ployed as a good template for fabricating metal oxide nanoparticles [20–25]. The existence
conditions of the Creative Commons
of many binding sites, notably NH2 and OH groups along the chains, is responsible for
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
chitosan’s high adsorption capability. That explains why it is so good at forming stable
4.0/).
complexes with metal ions and metal oxides [15–18,20,21]. On the other hand, among

Catalysts 2022, 12, 964. https://doi.org/10.3390/catal12090964 https://www.mdpi.com/journal/catalysts

Catalysts 2022, 12, 964 2 of 11

all metal oxides, copper oxide nanoparticles (CuONPs) have gained more attention due
to their unique properties, as an inexpensive and efficient heterogeneous catalyst, and
various applications [26].
Copper oxide nanoparticles’ catalytic activity allowed them to be used as a potent base
catalyst in aromatic nucleophilic substitution processes [6,7] and in various heterocyclic
synthesis methods [8–16]. In nucleophilic substitutions, Jammi et al. described a simple,
general, and efficient procedure for the cross-coupling of nitrogen, oxygen, and sulfur
nucleophiles with aryl iodides using CuO nanoparticles under ligand-free conditions [6].
On the other hand, Kidwai et al. have developed an economical method for the synthesis
of 3-arylpentane-2,4-diones and diethyl 2-aryl-malonates has been developed using CuO-
nanoparticles as the catalyst [7]. Satish et al. have developed a nanocrystalline CuO
catalyzed coupling of 2-iodoaniline, carbon disulfide, and nitrogen nucleophile under
ligand-free conditions in good yields [9].
Shaterian et al. have synthesized an efficient one-pot quantitative procedure for the
synthesis of benzo[a]pyrano[2,3-c]phenazine derivatives in the presence of nano CuO as
the catalyst [11].
Nitroolefins are useful organic compounds that are used as intermediates both in
synthetic chemistry and in industrial chemistry. They are commonly employed in various
carbon–carbon bond formations, including Diels–Alder cycloaddition, Michael reaction,
and Morita–Baylis–Hillman reaction. Furthermore, the nitro group may readily be trans-
formed into other useful functionalities. They are widely used in agrochemicals, materials,
medicines, and other industries. As a result, researchers are interested in developing effi-
cient procedures for the synthesis of nitroolefin. Recently, several useful approaches have
been established, mainly including nitration of vinylic C–H bonds, nitro-decarboxylation
of α, β-unsaturated aromatic carboxylic acids, and the traditional approach, particularly
the Henry reaction [27,28].
The Henry reaction is a classical name reaction known for more than a century. It
depends on base-mediated aldehyde or ketone condensation using nitroalkanes. The
extensive studies performed by organic chemists and the commercial availability of the
relatively low-cost starting materials make it a versatile and widely used reaction. Indeed,
the Henry reaction is one of the most simple and economical sets of reaction conditions
reported in the literature.
As a result of the aforementioned findings, we introduce an environmentally friendly
nitroolefin synthesis method using chitosan-CuO nanocomposites as an efficient heteroge-
neous base catalyst.

2. Materials and Methods

2.1. Apparatus and Instrumentations
Melting points were recorded on Gallen Kamp apparatus and are reported uncor-
rected. The Fourier Transform Infrared (FTIR) spectra were recorded in KBr pellets on a
JASCO FT-IR-6300 system at a resolution of 4 cm−1 , ranging from 400 to 4000 cm−1 . Field
Emission Scanning Electron Microscopy (FESEM) was carried out using a model Leo (Zeiss)
Remotely Operational Variable Pressure Field Emission SEM. The X-ray Diffraction (XRD)
measurements were performed at room temperature on a Siemens diffractometer model
D500 (Germany) operating in the reflection mode. Cu-Kα radiation (35 kV, 30 mA) was
used for the analysis. Microwave experiments were carried out using a CEM Discover
Labmate microwave apparatus (Discover, SP, NC, USA, 300 W). Sodium hydroxide was
purchased from Sigma-Aldrich (St. Louis, MO, USA). Triple distilled water was used in all
solution preparations. Chitosan of medium molecular weight and with 85% deacetylation
was purchased from Sigma-Aldrich. Copper oxide (nanopowder, <50 nm particle size
(TEM), 544868) was purchased from Sigma-Aldrich.
Catalysts 2022, 12, 964 3 of 11

2.2. Preparation of Chitosan-Based CuO Nanocomposite Films

Chitosan solution 2 w/v% was made by stirring chitosan (CS) in a 1 v/v% acetic acid
Catalysts 2022, 12, x FOR PEER REVIEW
solution for 12 h at room temperature on a magnetic stirrer. The pH of the3 resultant of 12
CS
solution was adjusted to the range of 6–7 by adding a calculated amount of 1 M NaOH
solution under continuous stirring after full dissolution. Then, under continuous stirring,
2.2. Preparation of Chitosan-Based CuO Nanocomposite Films
a suspension of 0.5 g CuO nanopowder in a small amount of double-distilled water was
Chitosan solution 2 w/v% was made by stirring chitosan (CS) in a 1 v/v% acetic acid
added portion by portion to the CS solution. The mixture was then subjected to microwave
solution for 12 h at room temperature on a magnetic stirrer. The pH of the resultant CS
irradiation at a power of 300, 400, and 500 watts for 3, 4, and 5 min, then the solution
solution was adjusted to the range of 6–7 by adding a calculated amount of 1 M NaOH
was solution
cast into a 100
under mm Petri
continuous dishafter
stirring andfull
dried overnight
dissolution. 70 ◦ C
Then,atunder in orderstirring,
continuous to remove any
traces of acetic acid.
a suspension of 0.5The CS-CuO
g CuO nanocomposite
nanopowder film was
in a small amount detached afterwater
of double-distilled complete
was drying,
rinsed withportion
added distilled water, to
by portion andthethen dried for
CS solution. h at 70 ◦was
The1 mixture C. Finally, characterizations
then subjected to micro- were
wave irradiation
performed at a power
on the formed of 300, 400, and 500 watts for 3, 4, and 5 min, then the solution
films.
was cast into a 100 mm Petri dish and dried overnight at 70 °C in order to remove any
traces of acetic
2.3. Synthesis acid. The CS-CuO nanocomposite film was detached after complete dry-
of Nitroolefin
ing, rinsed with distilled water, and then dried for 1 h at 70 °C. Finally, characterizations
Method
were A: In on
performed a conical flask,
the formed 10 mmol of aldehyde and 5 mmol of ammonium acetate
films.
were dissolved in 5 mL of nitromethane. The mixture was refluxed with stirring for
4–5 h2.3.
and the consumption
Synthesis of Nitroolefin of the aldehyde was checked by TLC. The reaction mixture
was evaporated
Method A: under vacuum
In a conical flask,and the residue
10 mmol wasand
of aldehyde dissolved
5 mmol ofinammonium
methylene chloride and
acetate
werewith
washed dissolved
water. in 5The
mL organic
of nitromethane. Thedried
layer was mixture wasfinally
and refluxed with stirringover
purification for 4–5 h
a short silica
and with
column the consumption
EtOAc: hexane of theasaldehyde
eluent was checked
afforded thebynitroolefin
TLC. The reaction
[29,30].mixture was
evaporated under vacuum and the residue was dissolved in methylene chloride and
Method B: The same procedure as Method A, using a chitosan-CuO nanocomposite
washed with water. The organic layer was dried and finally purification over a short silica
(15 wt.%) (0.1 g) instead of ammonium acetate and ethanol-water (70% solution), was used
column with EtOAc: hexane as eluent afforded the nitroolefin [29,30].
as solvent in thisB:reaction.
Method After 3–4ashMethod
The same procedure of refluxing the
A, using reaction mixture,
a chitosan-CuO the hot solution
nanocomposite
was (15
filtered
wt.%)to remove
(0.1 g) insteadchitosan-CuO nanocomposite
of ammonium acetate and the
and ethanol-water filtrate
(70% was was
solution), evaporated.
used The
residue was treated
as solvent with DCM
in this reaction. Afterand
3–4 hwashed withthe
of refluxing water. The
reaction organic
mixture, thelayer was dried and
hot solution
waspurified
finally filtered toover
remove chitosan-CuO
a short nanocomposite
silica column and thehexane
with EtOAc: filtrate was evaporated.
as eluent Theauthentic
to give
residue was treated with DCM and washed with water. The organic layer
samples of nitroolefin (m.p, mixed m.p, IR, and TLC). The catalyst film was removed from was dried and
finally purified over a short silica column with EtOAc: hexane as eluent to give authentic
the reaction mixture and thoroughly washed with ethanol before being dried and put to
samples of nitroolefin (m.p, mixed m.p, IR, and TLC). The catalyst film was removed from
use in
theadditional reactions.
reaction mixture and thoroughly washed with ethanol before being dried and put to
use in additional reactions.
3. Results and Discussion
3.1. Preparation of Discussion
3. Results and Chitosan-CuO Nanocomposite
3.1. Preparation
In fact, in ourofprevious
Chitosan-CuO Nanocomposite
work, we used the simple solution casting method to prepare
In fact, in our previous
the chitosan-copper work, we used thebut
oxide nanocomposite, simple solution
in this casting
paper, method to prepare
we attempted to modify this
methodology by using microwave irradiation to achieve a more homogeneous this
the chitosan-copper oxide nanocomposite, but in this paper, we attempted to modify distribution
methodology by using microwave irradiation to achieve a more homogeneous distribu-
of the copper oxide nanoparticles within the bulk of the polymer matrix. Thus, in this
tion of the copper oxide nanoparticles within the bulk of the polymer matrix. Thus, in this
article, the (CS-CuO) nanocomposite was prepared using a modified microwave assisted
article, the (CS-CuO) nanocomposite was prepared using a modified microwave assisted
simple solution
simple solution casting
castingprocess [15,16],asas
process [15,16], indicated
indicated in Scheme
in Scheme 1. 1.

OH
O O

OH
O
NH2 HO O
OH OH
OH
O O H2N
O O NHCOCH3
HO O CuO nanoparticles
HO CuO O
NH2 HO
OH HO
NH2
Chitosan H3COCHN
NH2
OH
O
O HO
O
O
HO

Scheme 1. Illustrative view of chitosan-CuO nanocomposite.

 Catalysts 2022, 12, x FOR PEER REVIEW

Catalysts 2022, 12, 964 4 of 11

Scheme 1. Illustrative view of chitosan-CuO nanocomposite.

3.1.1. FTIR Characterization

3.1.1. FTIR Characterization
Infrared spectroscopy provides more structural information by the presence o
Infrared spectroscopy
sence of the mainprovides more structural
characteristic absorption information
bands that byhelp
the presence
to detect the or ab-
main funct
sence of the main characteristic absorption bands that help to detect the
groups in the compounds. Herein, the FTIR spectra were measured for chitosan (A), main functional
groups in the compounds.
nanoparticles Herein,
(B), and thechitosan-CuO
FTIR spectra were measured for
nanocomposites chitosan
(C), and they (A),areCuO
shown in F
nanoparticles (B), and chitosan-CuO nanocomposites (C),
1. The spectrum of pure CS [15–18,31] (A) revealed a broad and they are shown band in Figure
at 3426 1. −1 due t
cm
The spectrum ofintermolecular
pure CS [15–18,31] (A) revealed a broad band at 3426 cm −1 due to the inter-
H-bonding of the O-H stretching and NH2 stretching bands, that are
molecular H-bonding
lappedoftogether
the O-Hin stretching
the sameand NH2 Furthermore,
region. stretching bands, the that
amide arecharacteristic
overlapped bands
together in the clearly
same region.
visible at Furthermore,
υ = 1655 and 1604 cm−1 in the spectrum, whereas theclearly
the amide characteristic bands were CH bands thro
visible at υ = 1655 − 1
outandthe1604 cm were
CS chain in the spectrum,
clearly visiblewhereas the CH
at υ =−2915, bands
2876, and throughout
1370 cm the
−1. In
1 . In Figure 1B, for CuO nanopar-
CS 1B, for
Figure
chain were clearly visible at
nanoparticles, twoυ = 2915, 2876, and 1370 cm
peaks, one at 3418 cm of the O-H stretching and−the
−1 other at 1622
ticles, two peaks,
of one at 3418
the O-H cm−1 of
bending, the O-Hdue
appeared stretching and the of
to the presence other at 1622
a trace amount cm of 1 of the
water in the co
O-H bending, appeared due to the presence
oxide nanoparticles. There are of two
a trace
peaksamount
at 1381of water
cm-1 andin the
1060 copper oxide to the a
cm−1 linked
nanoparticles. There are two peaks at 1381 cm -1 and 1060 cm−1 linked to the asymmetric
metric C-O in the copper oxide structure. Additionally, the CuO spectra showed the
C-O in the copperence oxide
of twostructure. Additionally,
characteristic bands, − attheυ =CuO
606 spectra
and 456showed
cm−1 thatthe presence of
correspond to the exp
two characteristic bands, at υ = 606 and 456 cm 1 that correspond to the expected Cu-O
Cu-O stretching vibrations, in the−range of 620–420 cm −1 as previously reported [3
stretching vibrations,
which arein the range ofto620–420
attributed cm 1 asphase
the monoclinic previously
of CuOreported [32,33],Figure
nanoparticles. which1C, for th
are attributed to the monoclinic phase of CuO nanoparticles. Figure 1C,
brid chitosan-CuO nanocomposite, showed the noisy shape with the presence of the b for the hybrid
chitosan-CuO nanocomposite,
band at 3438 cm−1showed and thethe twonoisy shape with
characteristic the at
bands presence
2115 andof2362 the broad
cm−1 that are st
−1 and the two characteristic bands at 2115 and 2362 cm−1 that are strong
band at 3438 cmevidence for the coordination of CuO molecules within the binding sites (NH2 and
evidence for the coordination
groups) along the of CuO
chitosanmolecules
backbone. within the binding
Finally, the visible sites (NH
shift and
in 2the OH finger
chitosan
groups) along the chitosan backbone.
region, especially at 632 Finally, the visible shift in the chitosan fingerprint
and 502 cm−1, is strong evidence for structural changes cause
region, especially −1 , is strong evidence for structural changes caused by
theatincorporation
632 and 502 cm of copper oxide nanoparticles.
the incorporation of copper oxide nanoparticles.

Figure 1. FTIR of (A) chitosan, (B) CuO nanoparticles, (C) Chitosan-CuO nanocomposites (15 wt.%).
Figure 1. FTIR of (A) chitosan, (B) CuO nanoparticles, (C) Chitosan-CuO nanocomposites (15 w
3.1.2. X-ray Diffraction (XRD)
3.1.2.features
The structural X-ray Diffraction (XRD) (A), pure CuO nanoparticles (B) chitosan-
of native chitosan
CuO nanocomposites (15structural
The wt.%), and (C) were
features of analyzed using the
native chitosan (A),XRD
puretechnique as shown (B) chit
CuO nanoparticles
in Figure 2. TheCuO
chitosan (A) displayed(15
nanocomposites thewt.%),
fundamental
and (C)typical = 20◦ the
peak at 2θusing
were analyzed (17–23 ◦
XRD), techniqu
which was typical of the
shown in hydrated
Figure 2. crystalline
The chitosanstructure of chitosan
(A) displayed the reported earlier
fundamental [15–18].
typical peak at 2θ
In Figure 2B, the same characteristic peaks of both chitosan and CuO molecules, 2θ of
chitosan at 20◦ and for CuO nanoparticles at 35.6◦ and 38.8◦ [34], were interfered with
a clear shift, which confirms the coordination between CuO molecules and the chitosan
Catalysts 2022, 12, x FOR PEER REVIEW 5 of 12

(17–23°), which was typical of the hydrated crystalline structure of chitosan reported ear-
Catalysts 2022, 12, 964 5 of 11
lier [15–18]. In Figure 2B, the same characteristic peaks of both chitosan and CuO mole-
cules, 2θ of chitosan at 20° and for CuO nanoparticles at 35.6° and 38.8° [34], were inter-
fered with a clear shift, which confirms the coordination between CuO molecules and the
chain. Furthermore,
chitosan the Debye–Scherrer
chain. Furthermore, formula was
the Debye–Scherrer used to
formula wascalculate
used tothe averagethe
calculate grain
aver-
size from the XRD patterns [35]:
age grain size from the XRD patterns [35]:
−0.9
−0.9 × λ∗ 𝜆
𝐷(𝑛𝑚)
D (nm )= =
β·cos
. cos
θ Ɵ

where, D (nm):
(nm): represents
represents the
thecrystalline
crystallinesize
sizeininnm,
nm,λ λis isthethe wavelength
wavelength of of Cu-Kα
Cu-Kα 1 =1 =
◦ , β can be calculated for the most intense peak for the CS-CuO nanocomposite
1.54060 A
A°, calculated for the most intense peak for the CS-CuO nanocomposite
Applying the
pattern. Applying the equation,
equation,the
theaverage
averageparticle
particlesize
sizewas
wasfound toto
found bebe
35.2 nm.
35.2 nm.

Figure
Figure 2. XRD of chitosan
chitosan (A),
(A),and
andchitosan-CuO
chitosan-CuOnanocomposite,
nanocomposite, (15
(15 wt.%)
wt.%) (B).
(B).

3.1.3. SEM
3.1.3. SEM and
and Morphological
MorphologicalChanges
Changes
SEM images were used to investigate the morphological alterations of CS-CuO nanocom-
posites in comparison to unmodified chitosan. As shown in Figure 3, the nonporous,
smooth membranous phase of chitosan (A) contained dome-shaped orifices, microfibrils,
 Catalysts 2022, 12, x FOR PEER REVIEW 6 of 12

Catalysts 2022, 12, 964

SEM images were used to investigate the morphological alterations of CS-CuO 6nano- of 11

composites in comparison to unmodified chitosan. As shown in Figure 3, the nonporous,

smooth membranous phase of chitosan (A) contained dome-shaped orifices, microfibrils,
and
andcrystallites,
crystallites,as
asshown
shownininthe
theSEM
SEMimage
image[15–18].
[15–18].On
Onthe
theother
otherhand,
hand,the
theimage
imageof
ofthe
the
CS-CuO
CS-CuOnanocomposite
nanocomposite(B)(B) exhibited distinct
exhibited modifications
distinct due due
modifications to coordination with CuO
to coordination with
molecules that are
CuO molecules uniformly
that dispersed
are uniformly over the
dispersed chitosan
over surface.
the chitosan surface.

Figure3.3.SEM
Figure SEMof
ofchitosan
chitosan(A),
(A),and
andchitosan-CuO
chitosan-CuOnanocomposites,
nanocomposites,(15
(15wt.%)
wt.%)(B).
(B).

3.1.4.
3.1.4.Energy-Dispersive
Energy-DispersiveX-ray
X-raySpectroscopy
Spectroscopy(EDS)
(EDS)and
andEstimation
EstimationofofCopper
Copper
Figure
Figure 44shows
showsan anEDS
EDSgraph
graphofofchitosan-CuO
chitosan-CuOnanocomposites
nanocomposites that
that was
was used
usedtoto
quantify
quantify the
the copper within the
copper content within thechitosan.
chitosan.The
The hybrid
hybrid material’s
material’s EDSEDS revealed
revealed the
the appearance
appearance of of
thethe standard
standard CuCusignals,
signals,which
whichindicated
indicatedthe
the amount
amount of copper inin the
the
chitosan matrix. As shown in Figure 4, the Cu content in the prepared sample was about
13.62 (wt.%).
atalysts 2022, 12, x FOR PEER REVIEW 7

chitosan matrix. As shown in Figure 4, the Cu content in the prepared sample was ab
Catalysts 2022, 12, 964 7 of 11
13.62 (wt.%).
Catalysts 2022, 12, x FOR PEER REVIEW 7 of 12

chitosan matrix. As shown in Figure 4, the Cu content in the prepared sample was about
13.62 (wt.%).

Figure 4. EDS
Figure 4. ofchitosan-CuO
EDS of chitosan-CuO nanocomposites
nanocomposites (15 wt.%).
(15 wt.%).
Figure
3.2.4.CS-CuO
EDS ofNanocomposite
chitosan-CuO nanocomposites
Film (15 wt.%).
as Basic Heterogeneous Catalyst in Synthesis of Nitroolefin
3.2. CS-CuO Nanocomposite Film as Basic Heterogeneous Catalyst in Synthesis of Nitroolefin.
3.2.1. Optimization of the Reaction Conditions
3.2.1. Optimization of the Reaction Conditions
3.2. CS-CuO Nanocomposite
Compound 1awas
Compound 1a
Film
wasselected
selected asa Basic
as as model
a model
Heterogeneous
compound
compound
Catalyst
foroptimization
for the the in Synthesis
optimization of Nitroolefi
of the experi-
of the exper-
mental
3.2.1. conditions.
Optimization
imental CS-CuO
conditions. of was selected
selected
the Reaction
CS-CuO was asasthe
thecatalyst
Conditions catalystforforthe
the optimization
optimization reactions. The
reactions.
basic character
The basic of this
character catalyst
of this and
catalyst andthe
thecatalytic
catalytic activity ofcopper
activity of copperoxide
oxide nanoparticles pro-
nanoparticles
Compound
moted us toususe
promoted 1a
to use was
it asit a selected
aaspowerful
powerful as ainmodel
catalyst
catalyst compound
comparison
in comparison to for the
toammonium
ammonium optimization
acetate
acetate of the ex
(experimental
(exper-
imental conditions. CS-CuO was selected as the catalyst for the optimization reacti
Section
imental2.3) in
Section the nitroaldol
2.3) in the condensation
nitroaldol reaction
condensation (Scheme
reaction 2)
(Scheme 2)
The basic character of this catalyst and the catalytic activity of copper oxide nanoparti
CS-CuO in comparison to ammonium acetate (ex
promoted us to use it as a powerful catalyst
O + H3 C NO2
imental Section 2.3) in the nitroaldol EtOH-H
condensation
2O
reaction (Scheme
NO2 2)
1a
Scheme 2.
Scheme 2. Nitroaldol
Nitroaldolcondensation
condensationreaction.
reaction. CS-CuO
O + H3 C NO2
The nature
The natureofofthe solvent
the andand
solvent catalyst loading
catalyst EtOH-H
have both
loading have Ooptimized
been
2both
and the re-and the
been optimized NO2
sults obtained are reported in Table 1 and Figure 5.
results obtained are reported in Table 1 and Figure 5.
Nature of Solvent 1a
Table 1. Henry reaction of benzaldehyde and nitromethane catalyzed by CS-CuO: effect of the solvent a .
In the screening of the solvents (Table 1), different solvents were studied, including
SchemeEntry2. Nitroaldol
nonpolar, polar
Catalyst condensation
protic, and aprotic
(mol%) reaction.
solvents.
Solvent THF Time
and toluene
(h) exhibited (◦ C)
the lowest
Temperature cata-
Yield (%)
lytic
1 results. This10could be explained THFby the fact that3 the charged intermediate
120 formed 8
The 2 nature of
during the reactionthe
10
can’tsolvent andeither
be stabilized
Toluenecatalyst loading
in an aprotic
3 have
polar or in both
120 been optimized
a nonpolar solvent.
13 and the
Ethanol showed very poor yield to the desired nitroolefin. However, ethanol-water mix-
sultsture
obtained
3 are10reported
as solvent showed
in Table
DMF 1 and Figure
the best result
5.
which suggests3 that water molecules
120
are essential 20
for 4enhancing the10basicity of CuOCH 3 CN
nanoparticles. The 3other three tested 120
polar aprotic sol- 25
Nature 5ofshowed
vents Solventpoor
10 results. Thus, we selected an ethanol-water
EtOH 3 mixture 120
as the best choice 14
for 6this reaction. 10 EtOH-H O (1:1) 3 120 58
In the screening of the solvents 2
(Table 1), different solvents were studied, includ
7
nonpolar, polar protic, and aprotic solvents. 3THF and toluene
10 EtOH-H2 O (1:3) 120
exhibited65the lowest c
8a 10 EtOH-H2 O (1:5) 3 120 80
lytica Experimental
results. This could be explained by the fact that the charged intermediate form
conditions: catalyst CS-CuO (wt.% = 10), T = 120 ◦ C, and reaction time = 3 h.
during the reaction can’t be stabilized either in an aprotic polar or in a nonpolar solv
Ethanol showed very poor yield to the desired nitroolefin. However, ethanol-water m
ture as solvent showed the best result which suggests that water molecules are essen
for enhancing the basicity of CuO nanoparticles. The other three tested polar aprotic
 Amount of Catalyst (Catalyst Loading)
We initially set the catalyst/benzaldehyde weight percent (wt.%) to be 5. The ni-
troolefin 1a was successfully isolated from the reaction mixture and its structure has been
Catalysts 2022, 12, 964 fully identified by NMR, mass spectroscopy, and elemental analysis. 8 of 11

100

300

80 250

Time (min)
%Yield

200
60

Loading of Catalyst vs. %Yield

Loading of Catalyst vs. Time (min.) 150

40
0 5 10 15 20 25

Loading of Catalyst wt%

Figure 5. Henry
Henry reaction
reactionof
ofbenzaldehyde
benzaldehydeand andnitromethane
nitromethanecatalyzed
catalyzedbyby
CS-CuO:
CS-CuO:Optimization of
Optimization
catalyst loading (wt.%). Experimental conditions: catalyst CS-CuO (wt.% = 5–20), solvent
of catalyst loading (wt.%). Experimental conditions: catalyst CS-CuO (wt.% = 5–20), solvent = = EtOH-
H2O (1:5),OT(1:5),
EtOH-H = 120T°C, and◦ C,
= 120 reaction time = 3time
and reaction h. = 3 h.
2

NatureAsof Solvent
shown in Figure 5, the catalyst loading of 15 wt.%. was found to be the optimal
quantity, as this percentage
In the screening of catalyst
of the solvents provided
(Table the highest
1), different yield
solvents of product
were studied,1aincluding
(90%) in
3 h. After polar
nonpolar, the reaction wasaprotic
protic, and complete, the used
solvents. THFcatalyst film exhibited
and toluene was detached, purified
the lowest with
catalytic
hot ethanol,
results. This and
couldrecovered to be by
be explained usefully utilized
the fact that thefour more intermediate
charged times with minor lossduring
formed in cat-
alytic
the activity
reaction (Figure
can’t 6).
be stabilized either in an aprotic polar or in a nonpolar solvent. Ethanol
showed very poor yield to the desired nitroolefin. However, ethanol-water mixture as
solvent showed the best result which suggests that water molecules are essential for
enhancing the basicity of CuO nanoparticles. The other three tested polar aprotic solvents
showed poor results. Thus, we selected an ethanol-water mixture as the best choice for
this reaction.

Amount of Catalyst (Catalyst Loading)

We initially set the catalyst/benzaldehyde weight percent (wt.%) to be 5. The ni-
troolefin 1a was successfully isolated from the reaction mixture and its structure has been
fully identified by NMR, mass spectroscopy, and elemental analysis.
As shown in Figure 5, the catalyst loading of 15 wt.%. was found to be the optimal
quantity, as this percentage of catalyst provided the highest yield of product 1a (90%) in
3 h. After the reaction was complete, the used catalyst film was detached, purified with hot
Catalysts 2022, 12, x FOR PEER REVIEW 9 of 12
ethanol, and recovered to be usefully utilized four more times with minor loss in catalytic
activity (Figure 6).

Figure 6. Recyclability of CS-CuO (15 wt.%) nanocatalyst in synthesis of product 1a.

Figure 6. Recyclability of CS-CuO (15 wt.%) nanocatalyst in synthesis of product 1a.
By summing up the data from the optimization, the best result was obtained by em-
ploying CS-CuO (15 wt.%), at 120 °C for 3 h in (1:5) EtOH-H2O as the solvent.

3.2.2. Scope of the Reaction

The scope of the reaction has been explored (Table 2). Different substituted benzal-
dehydes and nitroalkanes were subjected to our optimum conditions. It is interesting to
Catalysts 2022, 12, 964 9 of 11
Figure 6. Recyclability of CS-CuO (15 wt.%) nanocatalyst in synthesis of product 1a.
Figure 6.Recyclability
Figure Recyclability ofCS-CuO
CS-CuO (15wt.%)
wt.%) nanocatalystininsynthesis
synthesis ofproduct
product 1a.
Figure 6.
6. Recyclability of
of CS-CuO (15
(15 wt.%) nanocatalyst
nanocatalyst in synthesis ofof product 1a.
1a.
By
Figure
By summing 6.summing
up6. up
Recyclability ofthe data
CS-CuO from the
(15 wt.%) optimization,
nanocatalyst the best
in synthesis ofresult was
product 1a.obtained b
Figure Bythe
By
data from
Recyclability
summing
summing up thedata
of CS-CuO
theup
optimization,
(15 wt.%)
from
the
the bestinresult
thenanocatalyst
optimization, was
synthesis
the best of obtained
product
result by
was1a.obtained by
ploying
employing CS-CuO (15CS-CuO
By summing
wt.%), (15
at up
120the◦ Cdata
wt.%), at 3from
data
for 120
from
h in°Cthe
the optimization,
for 3EtOH-H
optimization,
(1:5)
the
h in (1:5)OEtOH-H
the best result
2O as the
bestsolvent.
as the result was obtained
obtained by
wassolvent. by em
e
ploying
By
ploying CS-CuO
summing
CS-CuO (15
up
(15 wt.%),
the
wt.%), dataatat 120
from
120 °C°C
the for
for 3 3hhinin(1:5)
optimization, (1:5)
2 EtOH-H
the
EtOH-Hbest 2O
2O as the solvent.
result
as was
the obtained
solvent. by em
ploying CS-CuO (15 wt.%), at 120 °C for 3 h in (1:5) EtOH-H
By summing up the data from the optimization, the best result was obtained by em 2 O as the solvent.
ploying
3.2.2. Scope of3.2.2.
the Scope
ReactionCS-CuOof the(15 wt.%), at 120 °C for 3 h in (1:5) EtOH-H2O as the solvent.
Reaction
ploying
3.2.2. CS-CuO
Scope ofthe (15
the wt.%), at 120 °C for 3 h in (1:5) EtOH-H2O as the solvent.
Reaction
3.2.2.
3.2.2. Scope
Scope of
of the Reaction
Reaction
The scope3.2.2. The
of the scope
reaction of
has the reaction
been exploredhas (Table
been explored
2). Different (Table 2). Different
substituted substituted be
benzalde-
Thescope
Scope scope
of the ofReaction
the reaction hasbeen
been explored (Table 2).Different
Different substitutedbenz ben
3.2.2. The
dehydes
hydes and nitroalkanes Scope
The scope
and
were
of
the the
the reaction
ofnitroalkanes
of Reaction
subjected reaction
towere
our
has
has been explored
subjected
optimum explored
to our
conditions.
(Table
(Table
optimum
It
2).
2).interesting
is Different
conditions.substituted
substituted
to note benz
Itisisinterestin
interesti
dehydes
The scope
dehydes and
and nitroalkanes
of the reaction
nitroalkanes were
were has subjected
been explored
subjected toto our optimum conditions.
(Table 2). conditions. It
Different substituted benza
that the reaction dehydes
note that
The
was andreaction
the
scope
found nitroalkanes
ofbe
to was
thetolerant
reaction were
found
tohassubjected
bothto
beenbe to our
tolerant
explored
electron our optimum
optimum
to both
(Table
donating 2).
(NMeconditions.
electron
Different
It
It
donating
2 , OCH
is
is interesting
substituted
3 , and
interesting
(NMe 2, O
benza
note
dehydes
note that
that and thenitroalkanes
the reaction
reaction was
was found
were
found tobe
subjected
to betolerant
tolerant
to our toboth
bothelectron
optimum
to electron
conditions. donating
It
donating is (NMe 2, OC
interesting
(NMe 2, OCH
and
CH3 ) and electronnote
dehydes
CH that the
and reaction
nitroalkanes
3) and electron
attracting groups was found
were
attracting
(F, Cl, Br, and to be
subjected
groups tolerant
NO2(F, to
)(F, our
Cl,
that to
Br, both
optimum
and electron
NOin 2) that donating
conditions. It is
arepresent
present (NMe ,
interesting
ringininthe2 OCH
thephe
p
noteand CH
that 3) and
3)the
electron attracting groups Cl,are present
Br,andandNO NO the phenyl
2) that are
and
andof
note
ring
of benzaldehyde.
CH
CH
that andreaction
and
3)the
benzaldehyde. electronwas
electron
reaction
foundgroups
attracting
attracting
was
to
found groups
be tolerant
(F,
(F, Cl,
to be tolerant
to
Cl, Br,
Br, both
to and
bothNO
electron
2) that aredonating
are present
2) that donating
electron present (NMe
in
in the
(NMe
2, phen
the OCH
phen
2, OCH
and ring of benzaldehyde.
ringCH
ring
and
of 3) and electron attracting groups (F, Cl, Br, and NO2) that are present in the phen
of benzaldehyde.
CH 3benzaldehyde.
) and electron attracting groups (F, Cl, Br, and NO2) that are present in the phen
ring of benzaldehyde.
ring
Table
Table 2. Scope of the of2.benzaldehyde.
Scope
reaction.
Table 2. Scope ofofthethereaction.
reaction.
Table
Table 2. 2. Scope
Scope of of the
the reaction.
reaction.
Table 2. Scope of the reaction.
Table 2. Scope of the reaction.

Entry
Entry R1RR1 RR R2 R2 Product
Product Yield
Yield(%)
Entry
Entry EntryR11 R1 R222 Product
Product
Product Yield (%)Yield
Yield (%)(%)
(%)
Entry R1 R2 Product Yield (%)
Entry R1 R2 Product Yield (%)
1 11 1 4-Cl
4-Cl
14-Cl
4-Cl 4-Cl CH
CHCH3
CH333 CH3 65 65
65
65 65
1 4-Cl CH3 65
1 4-Cl CH3 65

2 4-F CH3 72
2 22 4-F
24-F
4-F 4-F CH
CH
CH333 CH3 72 72
72 72
2 4-F CH3 72
2 4-F CH3 72

33 4-NO
4-NO 2
2 CHCH
CH 3-CH2
CH3-3-3-CH 2 6868
3 3 34-NO
4-NO 2 2 4-NO2 CH CH 22
CH 3- CH2 68 68 68
3 4-NO2 CH3-CH 2 68
3 4-NO2 CH3-CH2 68

44 3-Cl
3-Cl CHCH3
CH333 7474
4 44 3-Cl
3-Cl CH 74 74
4 3-Cl 3-Cl CH3 CH3 74 74
4 3-Cl CH3 74

55 5 3-Br
3-Br
3-Br CHCH3
CH33 7373
73
5 5 2022,
Catalysts
Catalysts 2022,12, FOR3-Br
12,xxFOR PEERREVIEW
REVIEW
3-BrREVIEW
PEER CH
CH33 73 73 10ofof
10
Catalysts
5 2022, 12, x FOR5PEER
3-Br 3-Br CH3 CH3 73 73 10 of

666 64-OCH3 4-OCH3

4-OCH CH3 CH3
CH 60 60
60
4-OCH33 CH33 60

777 4-CH3
74-CH
4-CH33 4-CH3
CH3
CH
CH33 CH3 66
66
66
66

888 4-NMe22
4-NMe
4-NMe
8 2 4-NMe2
CH3
CH
CH33 CH3 49
49
49
49

Experimentalconditions:
Experimental conditions:catalyst
catalystCS-CuO
CS-CuO(15(15wt.%),
wt.%),solvent
solvent==EtOH-H
EtOH-H2O,
2O, T = 120 °C, and reaction time = 3 h.
T = 120 ◦°C, and reaction time = 3 h.
Experimental conditions:
Experimental catalyst
conditions: CS-CuO
catalyst (15
CS-CuO (15wt.%),
wt.%),solvent
solvent ==EtOH-H
EtOH-H22O, T == 120
O, T 120 °C, andreaction
C, and reactiontime
time= =3 3h.h.

4.4.Conclusions
Conclusions
4. Conclusions4. Conclusions
The presentstudystudyusedusedaasimple
simplesolution
solutioncasting
casting approachto to efficientlyprepare
prepare ch
The
The present
present casting approach to efficiently prepare ch
The present study
tosan-copper
tosan-copper used astudy
oxide
oxide simple used
(CS-CuO)
(CS-CuO)
a simplecasting
solution solution
nanocomposite.
nanocomposite. approach approach
to efficiently
The produced
The produced
efficiently
prepare
nanocomposite
nanocomposite
ch
film wa
film w
chitosan-coppertosan-copper
oxide (CS-CuO) oxide (CS-CuO)
nanocomposite. nanocomposite.
TheFESEM,
produced The produced
nanocomposite nanocomposite
film was film w
thoroughly
thoroughly examined
examined usingFTIR,
using FTIR,XRD,
XRD, FESEM,and and EDSmeasurements.
EDS measurements. Theexistenc
The existen
thoroughly examined using FTIR, XRD, FESEM, and EDS measurements. The existen
thoroughly examined
ofof copper using
oxide FTIR, XRD, FESEM,
nanoparticles withinandtheEDS measurements.
chitosan The existence
matrix wasconfirmed
confirmed by allthethe too
of copper
copper oxide
oxide nanoparticles
nanoparticles withinwithin the
the chitosan
chitosan matrix
matrix waswas confirmed by by all
all the tool
too
of copper oxide data. Theexistence
existence
nanoparticles
data. The ofCuO
within
of CuO molecules
themolecules
chitosan was wasdemonstrated
demonstrated
matrix was confirmed byFTIR
by FTIR spectra
by spectra
all thatexhibited
the tools’
that exhibited
data. The existence of CuO molecules was demonstrated by FTIR spectra that exhibited
noticeable
data. The existence of CuO
noticeable alteration
moleculesin thewasfingerprint region.by
demonstrated In addition,
FTIR spectraboth that
chitosan and CuOchara
exhibited chara
noticeable alteration
alteration in in the
the fingerprint
fingerprint region.
region. In
In addition,
addition, both
both chitosan
chitosan andand CuOCuO chara
teristic
teristic peaks were visible in the XRD pattern. Furthermore, the SEM picture of the C
teristic peaks
peaks were
were visible
visible in in the
the XRD
XRD pattern.
pattern. Furthermore,
Furthermore, the the SEM
SEM picture
picture of of the
the CC
CuO
CuO nanocomposite revealed a clear uniform surface modification due to CuO molecu
CuO nanocomposite
nanocomposite revealed
revealed aa clear
clear uniform
uniform surface
surface modification
modification due due toto CuO
CuO molecu
molecu
coordination.This
coordination. ThisCS-CuO
CS-CuOhybrid hybridnanocomposite
nanocompositewas waseffectively
effectivelyemployed
employedas as anenven
coordination. This CS-CuO hybrid nanocomposite was effectively employed as an an env
ronmentally
ronmentally friendly heterogeneous basic catalyst in the manufacture of a high-impa
ronmentally friendly
friendly heterogeneous
heterogeneous basic basic catalyst
catalyst in
in the
the manufacture
manufacture of of aa high-impa
high-impa
nitroolefin.The
nitroolefin. Thecreated
createdcatalyst
catalystisisaapromising
promisingcatalyst
catalystnotnotonly
onlybecause
becauseof of itsnon-tox
non-tox
nitroolefin. The created catalyst is a promising catalyst not only because of its its non-tox
Catalysts 2022, 12, 964 10 of 11

a noticeable alteration in the fingerprint region. In addition, both chitosan and CuO
characteristic peaks were visible in the XRD pattern. Furthermore, the SEM picture of
the CS-CuO nanocomposite revealed a clear uniform surface modification due to CuO
molecule coordination. This CS-CuO hybrid nanocomposite was effectively employed as an
environmentally friendly heterogeneous basic catalyst in the manufacture of a high-impact
nitroolefin. The created catalyst is a promising catalyst not only because of its non-toxic
nature but also because of its economic impact, which means it might be employed in
the industrial manufacturing of the compounds mentioned. Finally, we conclude that the
nanocomposite base catalyst can be used to efficiently synthesize a variety of heterocycles
that have previously been generated via non-green methods.

Author Contributions: Data curation, M.A.E.-A., K.D.K. and A.H.B.; formal analysis, M.A.E.-A.,
K.D.K. and A.H.B.; investigation, M.A.E.-A., K.D.K. and A.H.B.; methodology, M.A.E.-A., K.D.K.,
and A.H.B.; resources, M.A.E.-A., K.D.K. and A.H.B.; software, M.A.E.-A. and K.D.K.; supervision,
M.A.E.-A., K.D.K. and A.H.B.; validation, K.D.K.; visualization, M.A.E.-A.; writing—original draft,
M.A.E.-A. and K.D.K.; writing—review and editing, M.A.E.-A., K.D.K. and A.H.B. All authors have
read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Data Availability Statement: Data are contained within the article.
Conflicts of Interest: There are no conflict to declare.

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