Production, characterization, and application of a novel chitosan-g-maleic anhydride and modified graphene oxide nanocomposite, supported methane sulfonic acid, for efficient synthesis of 1-(benzothiazolylamino) methyl-2-naphtols

Article abstract of DOI:10.1007/s11164-021-04538-z

An exceptionally productive and sustainable procedure is described in this paper to fabricate 1-(benzothiazolylamino) methyl-2-naphthols using a novel green nanocomposite of chitosan and diethylenetriamine-modified graphene oxide, supported methanesulfoni

Full text of DOI:10.1007/s11164-021-04538-z

Research on Chemical Intermediates
https://doi.org/10.1007/s11164-021-04538-z
Production, characterization, and application of a novel
chitosan‑g‑maleic anhydride and modifed graphene
oxide nanocomposite, supported methane sulfonic
acid, for efcient synthesis of 1‑(benzothiazolylamino)
methyl‑2‑naphtols
Nesa Lotf Far1 · Esmael Rostami1 · Ghasem Rezanejade Bardajee1
Received: 7 May 2021 / Accepted: 5 July 2021
© The Author(s), under exclusive licence to Springer Nature B.V. 2021
Abstract
An exceptionally productive and sustainable procedure is described in this paper to
fabricate 1-(benzothiazolylamino) methyl-2-naphthols using a novel green nano-
composite of chitosan and diethylenetriamine-modifed graphene oxide, supported
methanesulfonic acid (Ch@GO-DETA.MSA.). For the synthesis of the nanocom-
posite, maleic anhydride was frst attached to chitosan, and then, graphene oxide was
modifed by diethylenetriamine (GO@DETA). Subsequently, nanocomposite was
prepared from the reaction of chitosan-g-maleic anhydride and GO@DETA. Finally,
methane sulfonic acid was added to the nanocomposite to aford Ch@GO-DETA.
MSA. Structural properties of the nanocomposite were explored through various
techniques including X-ray difraction (XRD), thermal gravimetric analysis (TGA),
FTIR spectroscopy, scanning electron microscopy (SEM), and energy-dispersive
X-ray spectroscopy (EDS). 1-(Benzothiazolylamino) methyl-2-naphthols were ef-
ciently prepared in high to excellent yields through a multicomponent reaction of
2-aminobenzothiazole, aryl aldehydes, and 2-naphthol using Ch@GO-DETA.MSA.
nanocomposite under solvent-free conditions. The proposed protocol exhibited
superiority over several published protocols due to its nontoxicity and eco-friendly,
catalytic ability, short reaction times, generality, efciency, solvent-free condition,
and simple workup.
Keywords Chitosan · Graphene oxide · 1-(Benzothiazolylamino) methyl-2-
naphthols · Solvent-free synthesis · Nanocomposite · Nano-catalyst
*
Esmael Rostami
Esmaelrostami@gmail.com; e.rostami@pnu.ac.ir
1
Department of Chemistry, Payame Noor University, PO BOX, 19395-3697 Tehran, Iran
Vol.:(0123456789)
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N. L. Far et al.
Introduction
Multicomponent reactions (MCRs) are among the valuable assets in medicinal
chemistry, drug design, and drug exploration because of their high selectivity,
efciency, and simplicity [1]. The most important advantage of multicomponent
reactions is that the target molecules do not need to be purifed and the percent-
age of the by-products is very low. Multicomponent reactions can also decline the
amount of required reactant, solvent, and cost [2–5].
Solvent-free reaction contributes to an ideal synthesis due to economic (high
solvent price) and environmental (solvent risk to the environment) reasons. More-
over, rapid separation of products with no need for solvents will lead to faster
reaction rates due to the thickening of the reactants in the absence of solvent.
These points are of crucial signifcance during industrial production [6–8].
Chitosan is a polysaccharide composed of 2-amino-2-deoxy-d-glucopyranose
and [1,4]-linked 2-acetamido-2-deoxy-d-glucopyranose. Chitin biopolymer is
mainly extracted from marine sources with weak solubility in solvents. This prob-
lem can be resolved by partial deacetylation and the production of chitosan with
higher solubility [9]. Nontoxicity, high adsorption capacity, good biodegradabil-
ity, environmental compatibility, cost-efectiveness, multiple functional groups,
efcient absorption of dyes and metals, rapid kinetics, and the ability to derive
many derivatives are among the signifcant characteristics of chitosan. The prop-
erties of chitosan depend on its chemical nature including its degree of decontam-
ination and deacetylation, molecular weight, crystallinity, and the ionic charge of
amine functional groups [10, 11].
On the other hand, graphene oxide (GO) is a smooth sheet of carbon with
extraordinary mechanical, electrical, and optical properties [12–14]. Further-
more, GO is nontoxic and possesses various functional groups, making it a valu-
able candidate for the removal of molecules and ions from aquatic environments.
Graphene oxide can be dispersed in the chitosan matrix through the formation of
amide linkages [15]. Chitosan is a natural polymer with distinctive characteristics
including nonantigenicity, biological renewability, biodegradability, and biocom-
patibility [16–18]. Therefore, the functionalization of GO-DETA with chitosan-
g-maleic anhydride is a promising approach for reaching a novel nanocomposite
with exceptional properties of both materials.
Benzothiazole is an important heterocyclic system with critical signifcance in
organic synthesis and medicinal chemistry. These heterocyclic compounds form
the structural unit of numerous drugs such as astemizole [19], albendazole [20],
omeprazole [21], and mebendazole [22]. Benzothiazole derivatives have shown
considerable features including antimalarial [23], antifungal [24], anti-tubercular
[25], anti-infective and herbicide [26], anticancer [27], and antimicrobial [28]
activities. For this purpose, diverse catalysts containing [Fe3O4@SiO2@(CH2)3-
urea-SO3H/HCl] [29], RHA-[pmim]HSO4 [30], agar [31], ultrasound-promoted,
H2O/HPA [32], [PVP-SO3H] HSO4 [33], and NaHSO4.H2O [34] have been uti-
lized for the production of 1-(benzothiazolylamino) methyl-2-naphthols. These
procedures sufer from a series of disadvantages such as elevated temperatures
1 3

Production, characterization, and application of a novel…
and severe processes, toxic and expensive catalysts, long duration, need for
poisonous solvents, huge amounts of by-products, and tedious workup. Thus,
research on exploring novel protocols for the synthesis of mentioned heterocycles
has gained signifcant attention.
In this study, the productive construction of 1-(benzothiazolylamino) methyl-
2-naphthols as biologically active products was studied using a green and sustain-
able nanocomposite produced from chitosan and graphene oxide derivatives. The
protocol follows green chemistry principles including solvent-free conditions, ef-
cient reaction rates, higher yields, nontoxicity, inexpensive promoter, and moderate
conditions.
Results and discussion
In this research, partially N-maleated chitosan [35] and diethylenetriamine-function-
alized graphene oxide nanocomposite [36] were prepared and activated using meth-
ane sulfonic acid. The resulting nanocomposite was successfully used as an envi-
ronmentally benign catalyst in a multicomponent one-pot process for the synthesis
of 1-(benzothiazolylamino) methyl-2-naphthols under solvent-free conditions. To
examine the stability and durability of the nanocomposite, it was successively recov-
ered and reused for fve runs. The process exhibited a series of advantages including
the use of carbon and biopolymer-based nanocomposite (catalyst), solvent-free con-
dition, absence of toxic metals, and easy storage and handling of catalyst.
Production of graphene oxide and diethylenetriamine‑functionalized graphene
oxide
Graphene oxide was produced according to the improved Hummers method
(Scheme 1) [37, 38]. To obtain exfoliated graphene oxide with single-layer structure
through purifcation process, after elimination of solvent using a centrifuge, deion-
ized water was utilized and the mixture was sonicated for 30 min. The obtained col-
loid was purifed with a centrifuge to ofer nanostructured graphene oxide. Dieth-
ylenetriamine-functionalized graphene oxide (GO@DETA) was prepared from
graphene oxide and diethylenetriamine using dicyclohexylcarbodiimide (DCC) and
trimethylamine as reagents (Scheme 1) as previously reported [36].
Preparation of partially N‑maleated chitosan
and diethylenetriamine‑functionalized graphene oxide (Ch@GO‑DETA)
nanocomposite
N-Maleated chitosan was synthesized as reported in [35] using chitosan and
maleic anhydride (Scheme 2). The nanocomposite was prepared from the reaction
of maleated chitosan and GO@DETA using EDC (Scheme 2). The reaction was
performed for 24 h in NMP at 130 °C. The fnal nanocomposite was purifed via
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N. L. Far et al.
Scheme 1 The synthesis of GO@DETA
Scheme 2 The synthesis of Ch@GO-DETA
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Production, characterization, and application of a novel…
centrifugation and washing with deionized water and hot ethanol. Finally, purifed
and dried nanocomposite was reached at low pressure at 50 °C.
Preparation of chitosan, diethylenetriamine‑functionalized graphene oxide,
and methane sulfonic acid nanocomposite (Ch@GO‑DETA.MSA)
The above-mentioned nanocomposite (Ch@GO-DETA) was dispersed in chloro-
form and ultrasonically treated to reach a colloidal solution. Then, methane sulfonic
acid was used and the reaction continued for 5 h. Ultimately, the purifed product
(Ch@GO-DETA.MSA) was provided via centrifugation and washing with chloro-
form solution to remove unreacted and physically adsorbed acids (Scheme 3). Ulti-
mately, the nanocomposite was dried at 50 °C at low pressure.
Characterization of nanocomposites
Characterization of Ch@GO-DETA and Ch@GO-DETA.MSA nanocomposites
was appropriately performed by various techniques including FTIR, EDX, FESEM,
XRD, TG, and DSC.
FTIR spectra
FTIR spectra of graphene oxide, GO@DETA, Ch@GO-DETA nanocomposite,
and Ch@GO-DETA.MSA nanocomposite are presented in Figs. 1 and 2. Accord-
ingly, the FTIR spectrum of GO shows bands related to various structural substitu-
ents (Fig. 1a). The bands at 1068 and 1178 cm−1 demonstrate ether groups. Also,
the bands at 1286 and 1577 cm−1 are indicative of the double bonds of aromatic
rings. Stretching vibrations of carbonyl groups of graphene appeared at 1720 cm−1
Scheme 3 The synthesis of Ch@GO-DETA.MSA
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N. L. Far et al.
Fig. 1 The FTIR spectra of (a) GO and (b) GO@DETA
Fig. 2 The FTIR spectra of a Ch@GO-DETA and b Ch@GO-DETA.MSA nanocomposites
1 3

Production, characterization, and application of a novel…
[39]. Furthermore, OH of alcoholic, phenolic, and acidic functional groups can be
observed at 3418 cm−1 as stretching vibrations. The epoxide vibrations probably
emerged at 844 and 876 cm−1. Moreover, CH bending vibrations can be related to
567 cm−1 band [40].
Figure 1b depicts the FTIR spectrum of GO@DETA. The stretching vibrations
of NH and OH functional groups in graphene oxide and diethylenetriamine moieties
appeared as a strong band around 3437 cm−1. Aliphatic CH vibrations of diethylen-
etriamine can be observed at 2857 and 2926 cm−1 [41]. Further, stretching vibra-
tions of double bonds of graphene structure appeared at 1635 cm−1. Also, stretching
vibration of the carbonyl groups of graphene oxide appeared at 1696 cm−1. Fur-
thermore, strong stretching vibrations of etheric groups can be identifed at 1082
and 1097 cm−1 [16]. Additionally, a band at 612 cm−1 can be assigned to diethylen-
etriamine NH or bending vibrations of aromatic double bonds on the GO@DETA
surface. This vibration is stronger compared to GO. Functionalization of graphene
oxide can be confrmed by aliphatic CH vibrations of diethylenetriamine in GO@
DETA at 2857 and 2926 cm−1. Furthermore, upon functionalization, graphene oxide
skeleton converted to graphene benzene rings with smooth structure as indicated by
stronger C=C vibrations in FTIR spectrum of GO@DETA. Another evidence for
functionalization of graphene is the redshift (bathochromic shift) of carbonyl band
at GO@DETA compared to GO, which shows the formation of amide functional
groups (Fig. 1a and b).
According to the FTIR spectrum of Ch@GO-DETA in Fig. 2a, broad and strong
stretching vibrations around 3430 cm−1 correspond to NH and OH vibrations in the
amide groups of chitosan and graphene oxide and diethylenetriamine and intramo-
lecular hydrogen bonds [42]. Also, aliphatic CH symmetric and asymmetric stretch-
ing vibrations in chitosan and diethylenetriamine appeared at 2924 and 2877 cm−1
[42]. These bands are the fngerprints of polysaccharides that appeared in FTIR
spectra of carrageenans, glucans, and xylan [43]. The presence of amides carbonyl
groups in GO@DETA and maleimide was established by vibration stretching bands
at around 1662 cm−1 and higher frequencies [43]. Further, bands at 1560 corre-
spond to NH of amide group [44]. Moreover, bands at 1404 and 1308 cm−1 can
be attributed to aromatic double bonds. The band around 1423 cm−1 indicates CH2
moiety. C–O–C etheric vibration bands in chitosan structure emerged at 1153 cm−1
[43]. Additionally, the bands at 1029 and 1068 cm−1 can be assigned to stretching
vibrations of etheric groups in chitosan and graphene oxide [43]. Furthermore, the
band at 659 cm−1 can be related to the bending vibrations of NH or aromatic dou-
ble bonds. The out-of-plane bending vibration of CH in the polysaccharide ring
appeared at 894 cm−1 [43].
FTIR spectrum of Ch@GO-DETA.MSA is shown in Fig. 2b. The band related to
the stretching vibrations of OH, NH, and hydroxyl of the SO3H group can be seen
at 3400 cm−1 [45]. Stretching vibrations of CH in polysaccharide rings and dieth-
ylenetriamine moieties can be observed at 2876 and 2924 cm−1 [45]. The absorp-
tion bands at 1695 cm−1 can be assigned to vibrations of carbonyl bonds of amides
on the graphene oxide surface [46]. A strong band at 1635 cm−1 corresponds to
+
maleimide and chitosan (acetyl) carbonyl bonds and NH3 groups on chitosan and
graphene oxide [47]. Stretching vibrations of C=C in graphene can be observed at
1 3

N. L. Far et al.
1527 cm−1. The absorption band at 1334 cm−1 can be regarded as a sign of C–N
amide bond vibration. The small bending vibration of N–H bonds can be seen at
1550 cm−1 [44]. The CH2 vibrations can be seen at~1420 cm−1 [45]. The CH3 sym-
metrical vibrations emerged at~1388 cm−1. The band observed at 1203 cm−1 can be
assigned to vibrations of C–O etheric groups in graphene oxide and chitosan [48].
Asymmetric stretching vibrations of C–O–C chitosan ring [43] and SO3 group [45]
can be observed at 1165 cm−1. Also, the bands of etheric [45] or SO3 [49] can be
seen at 1037 and 1065 cm−1. Moreover, the out-of-plane bending vibrations of CH
in the chitosan ring can be seen at 890 cm−1 [43]. Furthermore, NH or C–S bending
vibrations can be detected at 775 cm−1 [49]. As well, bands of SO3 group can be
determined at 524 and 551 cm−1 [49].
XRD spectra
XRD patterns of GO, GO@DETA, Ch@GO-DETA, and Ch@GO-DETA.MSA
are reported in Figs. 3 and 4. Graphene oxide showed two characteristic peaks at
2θ=9.55° and 20.5°. The former corresponds to graphene oxide, while the latter
indicates trace amounts of reduced graphene oxide (Fig. 3a). Reduced graphene
oxide was probably formed through exfoliation process in an ultrasonic bath for
preparation of single-layer nanostructured graphene oxide. Figure 3b reports the
XRD pattern of GO@DETA. As seen, the peak at 9.55° disappeared and new peaks
emerged at 15°–32° corresponding to new crystalline structures with various d-spac-
ings. This phenomenon shows the efect of functionalization on the crystallinity of
graphene oxide. Functionalized graphene oxide exhibited higher crystallinity com-
pared with pristine graphene oxide.
Fig. 3 XRD spectra of GO (a) and GO@DETA (b)
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Production, characterization, and application of a novel…
Fig. 4 XRD patterns of Ch@GO-DETA (a) and Ch@GO-DETA.MSA (b)
XRD pattern of Ch@GO-DETA nanocomposite (Fig. 4a) shows a broad peak
in the range of 10°–50°, indicating the amorphous structure of nanocomposite.
According to the XRD pattern of chitosan and reduced graphene oxide with broad
peaks in this area [50, 51], the structure of Ch@GO-DETA nanocomposite is
mainly amorphous. Several sharp peaks at 39°, 43°, 64° and 78° showed the par-
tial crystalline structure of Ch@GO-DETA nanocomposite. Thus, the XRD pat-
tern confrmed the presence of chitosan and reduced graphene oxide in the nano-
composite structure [52].
The XRD pattern of the Ch@GO-DETA.MSA nanocomposite is observed in
Fig. 4b. The amorphous structure can be confrmed due to the wide peaks in Ch@
GO-DETA.MSA nanocomposite as verifed by chemical sources [53].
FESEM images and EDS analysis
The Ch@GO-DETA and Ch@GO-DETA.CH3SO3H samples were examined
using FESEM analysis (Fig. 5). According to the images, the particle sizes lie
between 17–33 and 17–42 nm for Ch@GO-DETA (Fig. 5a) and Ch@GO-DETA.
MSA (Fig. 5b) nanocomposites, respectively. Also in both combinations, some
levels of uniformity were observed.
EDS analysis was utilized to explore elemental composition. The results are
demonstrated in Fig. 6, which confrmed the presence of C, N, and O on the
GO@DETA. As expected, the EDS spectrum of Ch@GO-DETA showed C, N,
and O elements (Fig. 7a), while C, N, O, and S were detected in Ch@GO-DETA.
MSA nanocomposite (Fig. 7b).
1 3

N. L. Far et al.
Fig. 5 SEM images of (a) Ch@GO-DETA, (b) Ch@GO-DETA.MSA
TGA, DTG, and DTA analysis of nanocomposite
Thermogravimetric analysis (TGA) and diferential thermogravimetric analy-
sis (DTG), as well as diferential thermal analysis (DTA), were employed to
study the thermal behavior of Ch@GO-DETA.MSA nanocomposite. The sample
was heated to 600 °C. The TGA diagram is shown in Fig. 8. According to the
TGA results, the catalyst is thermally stable up to 200 °C, making it suitable for
applications at temperatures as high as 200 °C. According to the DTG diagram
(a derivative of the TGA diagram), there are four regions of structural decom-
position and weight loss; the largest one was seen at 214 °C [52]. Presumably,
water and solvents evaporate in the frst weight loss at 74–100 °C. The weight
loss at 214 °C can be related to the loss of functional groups of chitosan [54]. The
1 3

Production, characterization, and application of a novel…
Fig. 6 EDX analysis of GO@
DETA
Fig. 7 EDX analysis of (a) Ch@GO-DETA, (b) Ch@GO-DETA.MSA
weight variations at 319 and 461 °C can be also assigned to the degradation of
the polymer and graphene structure. The amount of weight loss was 65.43% and
the residual yield was 34.57%, which indicates the stability of the sample. The
DTA diagram showed two endothermic reactions at 207 and 321 °C. Compar-
ing the TGA diagram with the DTA results, these two reactions are the isolation
of functional groups from the surface and destruction of chitosan and graphene
structures, respectively (Fig. 8).
1 3

N. L. Far et al.
Fig. 8 TGA, DTG, and DTA diagrams of Ch@GO-DETA.MSA
Synthesis of 4‑[4‑(4‑chlorophenyl)‑3‑aza‑2‑oxo‑propyloxy] benzaldehyde (3)
To prepare a new 1-(benzothiazole amino) methyl-2-naphthol (7n), frst, a new alde-
hyde derivative (3) was prepared from N-(4-bromophenyl)-2-chloroacetamide (1)
[55] and 4-hydroxy benzaldehyde (2). The reaction proceeded in acetonitrile under
1
refux conditions (Scheme 4). FTIR, H NMR, 13C NMR, and mass spectroscopy
were employed to defne the structure of 3. Based on the FTIR spectrum, the NH
band of the amine group can be seen at 3541 cm−1, while the stretching vibration
of phenolic hydroxide emerged at 3398 cm−1. Moreover, C=O vibration can be
detected at 1689 cm−1 and the aromatic double-bond vibrations are manifested at
1593, 1534, and 1442 cm−1. Furthermore, the bands at 1176 and 742 cm−1 can be
assigned to the vibration of etheric (C–O) and aromatic C–Cl groups, respectively.
1H NMR spectrum showed two protons for methylene, eight protons for the aromatic
region, one proton for aldehyde, and one proton for amide NH. On the other hand,
13C NMR exhibited one aliphatic carbon, 12 aromatic carbons, and two carbonyl
carbons for the amide carbonyl group and the aldehyde group. Thus, NMR spectra
Scheme 4 Synthesis of 3
1 3

Production, characterization, and application of a novel…
confrmed the structure of 3. Furthermore, the mass spectrum verifed the molecular
weight of 3 at m/z of 290 equivalent to (M+1)+.
Optimum conditions for the production of 1‑(benzothiazolylamino)
methyl‑2‑naphtols and scope of nanocomposite (catalyst)
For optimization, the reaction of 2-aminobenzothiazole, 4-chloro benzaldehyde, and
2-naphthol using nanocomposite (Ch@GO-DETA.MSA) was selected as a model
(Scheme 5). The process was carried out under diverse conditions, and the impacts
of fve variables (time, the reaction temperature, catalyst load, type of catalyst, and
solvent (or solvent-free condition)) were investigated. Ultimately, the optimum reac-
tion conditions involved the temperature of 80 °C using 0.028 g nanocomposite
under solvent-free medium for 10 min (Table 1, entry 5).
Thin-layer chromatography (TLC) (n-hexane/ethyl acetate, 4:1) was selected to
monitor the improvements. After cooling, the residue was dispersed in hot alcohol
and the nanocomposite was separated and the precipitate was washed with ethyl
acetate (3×15 mL) to yield the product. To study the generality of our nanocompos-
ite, diverse aldehydes were selected and the process was carried out under optimal
conditions to reach desired product (Scheme 6). Aromatic aldehydes with various
substituents including benzaldehyde (with no substituent), electron-releasing and
electron-accepting groups, or halogens were run with 2-aminobenzothiazole and
2-naphtoles and investigated in the presence of Ch@GO-DETA.MSA nanocom-
posite (Table 2). According to the fndings, aldehydes with electron-withdrawing
groups and halogens aforded higher yields of products as compared to the electron-
donating groups.
To confrm the structure of products, the melting points of previously reported
ones were measured and weighed up to the data reported elsewhere. On the other
hand, NMR spectroscopic methods and FTIR and elemental analysis were utilized
1
for some of them to identify their structures. H NMR spectrum of 7b showed 14
protons for the aromatic region and one methine proton, as well as one NH proton
for benzothiazole and one hydroxyl proton of 2-naphthol. Also, 13C NMR spectrum
determined one methine carbon and 22 carbons for aromatic region. Thus, NMR
Scheme 5 The model reaction for the synthesis of 7b
1 3

N. L. Far et al.
Table 1 Optimization of the nanocomposite loading, temperature, and time for the synthesis of 7b
Entry
Ch@GO-DETA.
MSA (g)
Solvent
Temp. (°C)
Time (min)
Yielda (%)
1
2
3
4
5
6
7
8
–
–
–
–
–
–
–
–
–
90
90
90
90
80
70
80
80
80
70
80
50
70
90
10
10
30
10
30
10
10
10
80
80
60
80
40
87
95
90
95
95
44
48
53
55
72
56
60
0.040
0.028
0.020
0.028
0.028
0.028b
0.028c
0.028d
0.028
0.028
0.028
0.028
9
–
10
11
12
13
EtOH
H2O
CHCl3
CH3CN
aIsolated yield
bGO
cGO@DETA
dCh@GO-DETA
Scheme 6 Production of 1-(benzothiazolylamino) methyl-2-naphtols
1
spectroscopy confrms the structure of 7b. Moreover, H NMR spectrum of 7l
reported 15 protons for aromatic region and methine group as multiplet in addition
to one proton for benzothiazole NH and one proton for 2-naphthol hydroxyl group.
Furthermore, the FTIR spectrum of 7m showed stretching vibration of NH and
OH at 3368 and 1543 cm−1, respectively. The band at 1454 cm−1 can be assigned
to vibrations of aromatic double bonds. The vibrations of etheric bonds can be seen
1
at 1269 and 1126 cm−1. C–Cl vibration also emerged at 752 cm−1. H NMR spec-
trum of 7m identifed a peak with an integral of three protons for one CH3 group as
singlet and three protons as singlet for another CH3 group. Additionally, 14 protons
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Production, characterization, and application of a novel…
Table 2 Production of 1-(benzothiazolylamino) methyl-2-naphtols using Ch@GO-DETA.MSA nano-
composite
Entry Aldehyde
Products Time (min) Yielda (%) M.p (°C)
Found
Report
1
C6H5
4-ClC6H4
4-MeC6H4
4-FC6H4
4-MeOC6H4
3-O2NC6H4
2,4-Cl2C6H4
3-MeOC6H4
3-BrC6H4
7a
7b
7c
7d
7e
7f
7g
7h
7i
10
10
15
20
20
30
25
20
10
15
15
15
20
30
95
95
92
92
90
96
90
91
98
92
91
91
88
90
202–204 200–202 [56]
210–212 209–213 [56]
185–187 182–184 [57]
174–175 174–176 [56]
174–175 172–174 [56]
192–194 190–192 [58]
208–209 206–207 [56]
185–187 184–186 [59]
202–203 203–205 [60]
199–200 197–199 [56]
217–219 218–220 [56]
201–202 200–202 [56]
176–179 176–178 [56]
187–189 This work
2
3
4
5
6
7
8
9
10
11
12
13
14
2-ClC6H4
7j
7k
7l
2-NO2C6H4
2,3-Cl2C6H4
3,4-(MeO)2C6H4
7m
4-ClC6H4NHCO2CH2C6H4 7n
aIsolated yield
were observed for the aromatic region and one proton for the methine group as mul-
tiplet in the 1H NMR spectrum. Also, one proton was detected for NH of benzothia-
zole as singlet and one proton was observed for the 2-naphthol hydroxyl group as a
singlet. Also, 13C NMR spectrum determined two methyl carbons, one methine car-
bon and 22 carbons for aromatic region. Thus, FTIR and NMR spectroscopy veri-
fed the structure of 7m.
Ultimately, the FTIR spectrum of 7n showed the stretching vibration of NH
and OH at 3541 and 3399 cm−1, respectively. Also, the vibration of the amide car-
bonyl group can be observed at 1690 cm−1, whereas the vibration of aromatic dou-
ble bonds emerged at 1593 and 1443 cm−1. Further, the bands related to the ether
groups can be seen at 1269 and 1177 cm−1 and the vibration of the aromatic C–Cl
bond was detected at 752 cm−1. Moreover, the 1H NMR spectrum showed two pro-
tons for the methylene group as singlet, 18 aromatic protons, and one methine pro-
ton as multiplet. Also, two NH protons were identifed as singlet and one hydroxyl
proton as a singlet. On the other hand, the 13C NMR spectrum reported two aliphatic
carbons and 14 aromatic and carbonyl carbons. In addition, elemental analysis con-
frmed the elemental composition of 7n. Thus, FTIR and NMR spectroscopy and
elemental analysis confrmed the structure of 7n.
Reaction mechanism
Scheme 7 shows the reaction mechanism. At frst, the aldehyde (5) was proto-
nated by the acidic (weak) hydrogen of the ammonium group to reach protonated
1 3

N. L. Far et al.
Scheme 7 A plausible mechanism for producing 1-(benzothiazolylamino) methyl-2-naphtols using Ch@
GO-DETA.MSA nanocomposite
aldehyde. Then, the anionic part of the nanocomposite (methanesulfonate) con-
tributed to removing the proton of 2-naphthol hydroxide (step 1). In step 2, acti-
vated 2-naphthol attacked the activated aldehyde group via a nucleophilic attack to
1 3

Production, characterization, and application of a novel…
aford intermediate 1. Furthermore, in step 3 a water molecule was removed and
utilized by the acidic and basic sites of the nanocomposite to obtain intermediate
2. Step 4 involved the activation of nitrogen of benzothiazole by methanesulfonate
group and its attack on the intermediate 2. Finally, 2-naphthol was protonated by the
nanocomposite, which eventually led to the production of 1-(benzothiazole amino)
methyl-2-naphthols.
Reusability of nanocomposite
To evaluate and demonstrate the reusability and stability of Ch@GO-DETA.MSA
nanocomposite, a one-pot reaction of 2-naphtole, 2-aminobenzothiazole, and
4-chloro benzaldehyde was carried out for fve runs under optimized conditions
(Fig. 9). The nanocomposite was isolated, washed several times (ethyl acetate), and
then dried under vacuum. In agreement with Fig. 9, the yield of the product did not
substantially change after fve times, suggesting the stability and durability of the
nanocomposite.
Superiority over other catalytic systems
The synthesis of 1-((benzo[d]thiazol-2-ylamino) methyl) naphthalen-2-ols was
previously reported. Table 3 shows the comparison of the present protocol with
those reported in the literature. Based on the data collected, the Ch@GO-DETA.
MSA nanocomposite is superior over other catalysts in terms of catalyst load, reac-
tion time, temperature, product yield, environmental compatibility, and workup
simplicity.
95
93
90
87
86
100
90
80
70
60
50
40
30
20
10
0
20
18
10
14
15
Run 1
Run 2
Run 3
Run 4
Run 5
Time(min)
Yeild
Fig. 9 The results of recyclability and reusability of Ch@GO-DETA.MSA nanocomposite
1 3

N. L. Far et al.
Table 3 Production of 1-(benzo[d]thiazol-2-ylamino) (phenyl) methyl) naphthalen-2-ol (7a) using
diverse catalytic systems
Entry Catalyst
Solvent
Tem-
Time (Min.) Yielda (%) [Ref.]
perature
(°C)
1
2
3
4
5
6
7
8
9
Fe3O4@SiO2–ZrCl2‐MNPs (0.030 g) Solvent-free 100
[(CH2)3SO3HMIM][HSO4] (10 mol%) Solvent-free 100
15
5
10
6
10
10
7
90 [61]
87 [62]
89 [63]
93 [64]
95 [65]
88 [34]
92 [66]
91 [60]
Maltose (20 mol%)
Solvent-free 80
Solvent-free 80
Solvent-free 80
Solvent-free 100
Solvent-free 80
Solvent-free 100
Solvent-free 80
[H-Suc]HSO4 (0.030 g)
Oxalic acid (20 mol%)
NaHSO4.H2O (10 mol%)
Citric acid (20 mol%)
IL-SO3H (3 mol%)
5
10
This catalyst (0.028 g)
95 [This work]
The reactions were carried out by the condensation of 2-naphthol, 2-aminobenzothiazole, and benzalde-
hyde
aIsolated yield
Experimental
Chemicals and instruments
The materials were purchased from Merck and Fluka. TLC monitoring was carried
out using silica gel SIL G/UV 254 plates. A Thermo Scientifc 9200 apparatus was
utilized for the measurement of melting points. A Shimadzu model IRPerstige-21
spectrometer was used to record IR spectra. Also, the Shimadzu model: XRD
6000 apparatus was employed to obtain XRD patterns. The particle morphology
was examined by the TESCAN electron microscope. Thermal gravimetric analysis
(TGA) was carried out at 25 to 600 °C under Ar atmosphere and heating rate of
10 °C min−1 using a TA apparatus (model Q 600). Elemental analysis was performed
by a CHN-O-Rapid Heraeus elemental analyzer. Additionally, a Bruker Avance 500
spectrometer was utilized to record NMR spectra, while an Agilent Technologies
5975C spectrometer was applied to obtain mass spectra using an MSD detector run
at ionization potential of 20 to 70 eV.
Synthesis of modifed graphene oxide, chitosan‑g‑maleic anhydride,
and methane sulfonic acid (Ch@GO‑DETA.MSA) nanocomposite
Production of diethylenetriamine‑functionalized GO (GO@DETA)
GO was produced according to the modifed Hammer’s method (Scheme 1) [38].
Diethylenetriamine was also functionalized with graphene oxide according to our
previous work (Scheme 1) [36]. Typically, graphene oxide (1.5 g) in dimethylfor-
mamide (30 mL) was sonicated in a 50-ml fask for 1 h at 30 °C using an ultra-
sonic bath. Subsequently, diethylenetriamine (1 ml), triethylamine (1 mL), and
1 3

Production, characterization, and application of a novel…
dicyclohexyl carbodiimide (DCC, 1 g) were charged and spun at 25 °C for 48 h.
Finally, distilled water (2 mL) and DMSO (20 mL) were charged and hot-fltered. In
the end, they were washed with hot alcohol and dried at room temperature to obtain
GO@DETA.
Synthesis of chitosan grafted maleic anhydride (Ch@MA)
A mixture of chitosan (1 g), N-methylpyrrolidine (NMP, 30 mL), and maleic anhy-
dride (0.1 g) was heated at 90 °C for 20 h under N2. After cooling, the resulting solid
powder was fltered and purifed by washing with ethanol and dried under vacuum to
aford chitosan-g-maleic anhydride (Scheme 2).
Preparation of modifed graphene oxide and chitosan‑g‑maleic anhydride (Ch@
GO‑DETA) nanocomposite
NMP (20 mL) was added to Ch@MA (1 g), and dispersion was sonicated for 60 min
at 60 °C using an ultrasonic bath. Similarly, the dispersion of GO@DETA (0.4 g) in
NMP (20 mL) was prepared and sonicated for 1 h at 50 °C. Then, the GO@DETA
colloidal solution was added to the chitosan solution. Moreover, after stirring com-
bined solution for 10 min at room temperature, EDC (0.3 g) was charged and the
reaction continued for 24 h at 130 °C. Finally, deionized water (30 mL) and alcohol
(20 mL) were charged, centrifuged, and rinsed by alcohol and deionized water, fol-
lowed by drying to aford Ch@GO-DETA nanocomposite (Scheme 2).
Synthesis of modifed graphene oxide, chitosan‑g‑maleic anhydride,
and methane sulfonic acid (Ch@GO‑DETA.MSA) nanocomposite
To CH@GO-DETA (1 g), dry chloroform (15 mL) was charged and sonicated for
30 min. After adding methane sulfonic acid (0.5 mL), the stirring was maintained
for 5 h. Ultimately, the matrix was centrifuged, rinsed with chloroform (2×15 mL),
and dried at room temperature to aford Ch@GO-DETA.MSA nanocomposite
(Scheme 3).
Synthesis of 4‑[4‑(4‑chlorophenyl)‑3‑aza‑2‑oxo‑propyloxy] benzaldehyde (3)
To N-(4-chloroaniline)-2-chloroacetamide (1 [55], 1 mmol, 0.247 g) in acetoni-
trile (25 mL) were added 4-hydroxy benzaldehyde (2, 1 mmol, 0.122 g) and potas-
sium carbonate (1 mmol, 0.14 g) (Scheme 4). The mixture was refuxed for 48 h
under N2. The progress was monitored using thin-layer chromatography (TLC).
Deionized water (60 mL) was added, and after fltration, the resulting crude was
recrystallized in alcohol to aford 3 in 92% yield. m.p. 120–121°C, FTIR (KBr) ʋ:
1
3541, 3398, 1689, 1593, 1534, 1442, 1330, 1269, 1238, 1176, 817, 752 cm−1. H
NMR (500 MHz, DMSO-d6) δ 4.87 (s, 2H, CH2), 7.19 (d, J=8.1 Hz, 2H), 7.39 (d,
J=8.2 Hz, 2H), 7.68 (d, J=8.1 Hz, 2H), 7.90 (d, J=8.2 Hz, 2H), 9.74 (s, 1H, NH),
9.88 (s, 1H, COH); 13C NMR (125 MHz, DMSO-d6) δ 66.5, 113.8, 114.6, 120.7,
1 3

N. L. Far et al.
126.7, 128.1, 128.6, 129.5, 131.2, 131.2, 136.8, 162.1, 165.5, 189.7, 190.7; MS (EI):
m/z 290 (M+1)+.
General procedure for the preparation of 1‑(benzothiazolylamino)
methyl‑2‑naphtols
For optimization, 4-chlorobenzaldehyde (1.0 mmol, 0.15 g), 2-aminobenzothia-
zole (1.0 mmol, 0.15 g), and 2-naphtol (1.0 mmol, 0.14 g) were charged to Ch@
GO-DETA.MSA (0.028 g) (Scheme 5). The process was carried out under various
conditions, and the infuence of four variables including time, reaction temperature,
catalyst load, and solvent (or solvent-free condition) was investigated. Ultimately,
the optimum conditions were defned as the reaction temperature of 80 °C, catalyst
load of 0.028 g, solvent-free medium, and reaction time of 10 min (Table 1).
The process was detected using TLC (n-hexane/ethyl acetate) (4:1). The precipi-
tate was dispersed in alcohol, the nanocomposite was collected, and the precipitates
were rinsed with ethyl acetate several times followed by drying under vacuum.
Selected spectral data of products
1‑(Benzo[d]thiazol‑2‑ylamino) (4‑chlorophenyl) methyl) naphthalen‑2‑ol (7e)
1H NMR (DMSO-d6) δ 7.02–7.81 (m, 15H, ArH, and 1H, methine), 8.87 (s, 1H,
NH), 10.23 (s, 1H, OH); 13C NMR (125 MHz, DMSO-d6) δ 53.3, 118.8, 119.0,
121.5, 121.7, 123.1, 124.2, 124.3, 126.0, 127.0, 128.5, 128.6, 129.2, 130.4, 131.3,
131.4, 132.6, 142.2, 152.5, 153.8, 158.2, 163.1, 166.8.
1‑((Benzo[d]thiazol‑2‑ylamino) (2,3‑dichlorophenyl) methyl) naphthalen‑2‑ol (7l)
1H NMR (500 MHz, DMSO-d6) δ 7.04–8.07 (m, 14H, 13H, Ar, 1H, methine CH),
8.97 (s, 1H, NH), 9.99 (s, 1H, OH).
1‑(Benzo[d]thiazol‑2‑ylamino) (3,4‑dimethoxyphenyl) methyl) naphthalen‑2‑ol (7m)
1
IR (KBr, cm−1): 3368, 2932, 1771, 1543, 1454, 1331, 1269, 1126, 822, 752; H
NMR (500 MHz, DMSO-d6) δ 3.61 (s, 3H, CH3), 3.67 (s, 3H, CH3), 6.76–7.96 (m,
15H, 14H, Ar, and s, 1H, methine), 8.82 (s, 1H), 10.16 (s, 1H); 13C NMR (125 MHz,
DMSO-d6) δ 53.7, 53.8, 56.1, 111.2, 111.3, 112.2, 118.6, 119.1, 119.3, 121.4, 121.5,
123.0, 124.4, 126.0, 126.7, 129.1, 130.0, 131.2, 132.8, 135.2, 148.1, 149.1, 152.7,
153.7, 166.8.
2‑(4‑((Benzo[d]thiazol‑2‑ylamino) (2‑hydroxynaphthalen‑1‑yl) methyl)
phenoxy)‑N‑(4‑chlorophenyl) acetamide (7n)
IR (KBr, cm−1): 3541, 3399, 3063, 2924, 1690, 1593, 1443, 1331, 1269, 1177, 818,
752; 1H NMR (500 MHz, DMSO-d6) δ 4.15 (s, 2H, CH2), 6.43–7.38 (m, 19H, 18H
1 3

Production, characterization, and application of a novel…
Ar, and 1H methine), 8.30 (s, 2H, 2NH), 9.69 (s, 1H, OH); 13C NMR (125 MHz,
DMSO-d6) δ 53.0, 67.3, 114.5, 118.2, 118.6, 118.8, 121.0, 121.1, 121.5, 123.1,
124.0, 125.5, 126.3, 127.4, 128.7, 129.6, 130.8, 132.2, 133.4, 135.2, 137.4, 137.9,
152.3, 153.3, 156.4, 166.4, 166.9; Anal. Calcd for C32H24ClN3O3S: C, 67.90; H,
4.27; N, 7.42%. Found: C, 67.81; H, 4.36; N, 7.53%.
Conclusion
An efcient procedure is introduced for the production of 1-(benzothiazolylamino)
methyl-2-naphthols (potentially interesting and biologically active heterocycles)
using a novel green nanocomposite bearing chitosan and graphene oxide. The
encouraging benefts of this protocol include moderate condition, fast reaction rates,
generality, convenient purifcation stage, inexpensive promoter, nontoxicity, and
easy handling of catalyst and efciency. The developed protocol follows the green
chemistry principles and can be used for designing novel chitosan–graphene nano-
composites for organic synthesis procedures and materials science.
Supplementary Information The online version contains supplementary material available at https://doi.
org/10.1007/s11164-021-04538-z.
Acknowledgements The authors would like to appreciate the Payame Noor University (PNU) Research
Council for supporting this research study.
Declarations
Confict of interest There are no conficts of interest to declare.
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