Fabrication of activated carbon sulfuric acid as an excellent and novel solid acid catalyst, evaluating its catalytic activity in synthesizing 1,8-dioxo-octahydroxanthenes and 14-aryl-14H-dibenzo[a,j]xanthenes

Article abstract of DOI:10.1007/s11164-021-04457-z

In this work, for the first time, a novel and innovative procedure has been utilized to chemically functionalize activated carbon (AC) based on the sulfonation reaction, which can be used in catalytic reactions as a strong solid acid. For this aim, AC mus

Full text of DOI:10.1007/s11164-021-04457-z

Research on Chemical Intermediates
https://doi.org/10.1007/s11164-021-04457-z
Fabrication of activated carbon sulfuric acid as an excellent
and novel solid acid catalyst, evaluating its catalytic
activity in synthesizing 1,8‑dioxo‑octahydroxanthenes
and 14‑aryl‑14H‑dibenzo[a,j]xanthenes
Alireza Marandi1 · Nadiya Koukabi1 · Mohammad Ali Zolfgol2
Received: 28 December 2020 / Accepted: 29 March 2021
©
The Author(s), under exclusive licence to Springer Nature B.V. 2021
Abstract
In this work, for the ꢀrst time, a novel and innovative procedure has been utilized to
chemically functionalize activated carbon (AC) based on the sulfonation reaction,
which can be used in catalytic reactions as a strong solid acid. For this aim, AC must
pass three steps of oxidation, reduction, and sulfonation, respectively. Therefore, the
AC ꢀrst was oxidized, then reduced by lithium aluminum hydride, and eventually
participate in the sulfonation reaction with chlorosulfonic acid. We utilized diverse
analytical techniques such as FT-IR, XRD, TGA, XPS, and neutralization titration
to characterize and conꢀrm our claim that activated carbon was functionalized. The
analysis results indicate that sulfonic acid groups were successfully anchored with
covalent bonds on the AC’s surface. The resulting catalyst was used to synthesize
1
,8-dioxo-octahydroxanthenes and 14-aryl-14H-dibenzo[a,j]xanthenes and showed
good activity and stability in these reactions. Also, the produced products showed
acceptable and good yields (87–97%). Reusability without loss of catalytic activity
and simple fabrication method are other advantages of this catalyst.
*
Nadiya Koukabi
n.koukabi@semnan.ac.ir
1
2
Department of Chemistry, Semnan University, 35131-19111 Semnan, Iran
Faculty of Chemistry, Bu-Ali Sina University, 6517838683 Hamedan, Iran
Vol.:(012
1
3456789)
3

A. Marandi et al.
Graphic abstract
Keywords Solid acid · Activated carbon · Xanthene · Green chemistry ·
Heterogeneous catalyst
Introduction
It is vivid to everyone that more attention should pay to more environmentally
friendly processes in today’s world, especially in the chemical industry [1, 2].
This trend focuses on what is known as "Green Chemistry" or "Sustainable Tech-
nology" [3, 4]. Catalysts can be considered one of the Green Chemistry pillars
because they can be directed to advanced technologies to reduce chemical pro-
cesses waste [1, 5–10]. For example, sulfuric acid is an extensively versatile cata-
lyst for producing various chemicals in the industry. Over 15 million tons of this
substance is exerted annually as a non-recyclable catalyst in diꢁerent industries to
produce various chemicals [11]. Remaining this catalyst in the reaction medium
may cause problems such as corrosion and damage to equipment, and the separa-
tion of this catalyst and its reuse requires unique and costly methods [12, 13]. So
a lot of products and energy are wasted. Among the types of catalysts, acid cata-
lysts have a signiꢀcant role in producing various industrial materials. Many reac-
tions are catalyzed by traditional mineral acids such as H SO , AlCl , HF, and
2
4
3
HCl. These reactants have many problems, including toxicity, transport hazards,
1
3

Fabrication of activated carbon sulfuric acid as an excellent…
storage, corrosivity, environmental damage, separation and cooling problems, and
regeneration costs [14–18]. These acids are usually soluble in the organic reac-
tion medium or remain as a separate phase and are eliminated during the water’s
cooling phase and require a signiꢀcant alkali volume for subsequent neutraliza-
tion. These problems limit the use of these catalysts in industry and necessitate
replacing these catalysts with more advanced ones [1]. Replacing traditional
mineral acids with solid acids is the right solution because solid acids do not
have the traditional mineral acid problems that cause limit their use in industry.
In recent decades, solid acids have been considered by many researchers. These
types of catalysts can be utilized in many diꢁerent reactions of acid-promoted [1,
1
1, 18–23]. They are green, stable, clean, and low-cost catalysts with low corro-
sion and higher selectivity and can be reused multiple times without loss of activ-
ity and easily removed from the reaction system for later use [24–28]. It has been
speciꢀed that the type of support material utilized in solid acids is a vital factor
in the eꢂciency of the generated supported catalyst in chemical reactions. There
are diverse organic|inorganic supports that can be utilized for this purpose, such
as silica, hydroxyapatite, zeolites, zirconia, polymers, and carbons [1]. Today,
carbonaceous materials play an undeniable role in green chemistry and environ-
mental studies [29–31]. Carbon-based solid acids are important for several rea-
sons, including their inexpensive, phase compatibility with organic environments,
abundance, and hydrophobicity. Amorphous carbon with sulfonic acid sites is a
promising embedment for the sulfuric acid catalyst [22].
For the ꢀrst time in this paper, we utilized activated carbon and generated acti-
vated carbon sulfuric acid (ACSA; AC-OSO H) as a heterogeneous solid acid.
3
Due to the small pore size, board pore distribution, and high speciꢀc surface area,
activated carbon has been utilized as an eꢂcient and functional material in this
catalyst. Aꢃuence, availability, cost-eꢁectiveness, non-toxic, phase compatibility
with organic media, and hydrophobicity are other advantages of activated carbon.
Benzoxanthenes and xanthenes are among the compounds that are of great impor-
tance due to their vast and vital applications in the biological and industry, such
as anti-inꢄammatory activities [32], antibacterial [33], antiviral [34], anticancer
[
35], leuco dyes [36], laser technology [37], and sensitizers in photodynamic
therapy [38]. Many methods have been reported to synthesize these two matters,
but these methods have drawbacks such as harsh reaction conditions, prolonged
reaction time, excessive use of catalysts, and low eꢂciency [39–43]. Nowadays,
multi-component reactions (MCRs) have been considered to synthesize vari-
ous compounds, including xanthenes [44]. In multi-component reactions, three
or more reactants are combined in the same pot to produce the desired product.
These reactions do not require intermediate separation, so energy consumption
and reaction time are reduced. Compared to the multistage synthetic procedure,
MCRs are a powerful synthetic method for synthesizing heterocyclic compounds
due to their simplicity and high eꢂciency [45–47]. Therefore, in this paper, we
fabricate sulfuric acid-based activated carbon and investigate its catalytic activity
in synthesizing benzoxanthenes and xanthenes derivatives.
1
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A. Marandi et al.
Experimental
Materials and equipment
All chemicals utilized in this work were of the utmost purity purchased by Merck.
Activated carbon powder was (particle size: < 100 μm, about 90%) purchased
from Merck. Deionized distilled water was used throughout the work; X-ray dif-
fractometer analysis was performed by (XRD) (38066 RIVA, d/G. Via M. Mis-
one, 11/D (TN) ITALY) at room temperature. Mettler-TG 50 thermal analyzer
was utilized for TGA analysis, and temperature range and condition analysis were
2
5–400 °C and a heating rate of 10 °C/min under the nitrogen atmosphere. FT-IR
spectra were obtained from the Bruker IFS 66 FT-IR spectrometer in 400–4000
−
1
cm . X-ray information was gauged on an STOE IPDS-II two-circle diꢁractom-
eter at 120 K for high-resolution scans and survey scans. The pass energies were
2
0 eV and 160 eV, respectively. Titration was used to gauge the acidity of solid
samples.
Treatment of AC
Oxidation of AC
In order to manufacture the desired catalyst, the oxidation treatment process must
ꢀ
rst be accomplished on activated carbon. Oxidation treatment was done with
nitric acid because previous research has shown that nitric acid utilization makes
the carbon further acidic [48]. The reason for oxidation is to create sites and moi-
eties on the surface of activated carbon. Before oxidation, the purchased activated
carbon was ꢀrst rinsed with HCl (0.1 M) and NaOH (0.1 M) solutions to remove
alkaline and acidic impurities, respectively. In the next step, the washed activated
carbon was reꢄuxed for 2 h in a solution of 30% w–v nitric acid. Eventually, it
was rinsed with distilled water to achieve a neutral pH.
Reduction of AC
Lithium aluminum hydride (LiAlH ) was utilized to reduce oxidized AC. For this
4
purpose, 20 mg of oxidized AC was dispersed in toluene by ultrasonic appara-
tus (in a water bath) for 30 min, and then 5.0 mg of LiAlH is added gradually.
4
The resulting solution was stirred for an hour at ambient temperature, and then
followed 2.0 mL of HCl (2 N) was added to the solution until it removed the
remaining lithium and aluminum. Finally, the solution was ꢀltered, rinsed with
solvents of toluene, absolute ethanol, and acetone, respectively, and was placed in
a vacuum oven at 80 °C overnight until the reduced AC was produced.
1
3

Fabrication of activated carbon sulfuric acid as an excellent…
Sulfonation of AC
The equipment utilized for sulfonation of reduced AC was: Vacuum ꢄask attached
to the constant pressure dropping funnel and gas inlet tube. 220.5 mg (1.892
mmol) of chlorosulfonic acid was added dropwise to 1000 mg of reduced AC for
3
0 min at ambient temperature. HCl gas was immediately emitted from the reac-
tion container and removed through the gas inlet tube, and directed to water as
the adsorbent solution. After completion of the reaction, the creating compound
was shaken for 30 min. Finally, a black solid of activated carbon sulfuric acid
(
ACSA) was generated (Fig. 1).
Catalytic reaction
Synthesize of 14‑aryl‑14H‑dibenzo[a,j]xanthenes
The combination includes 2-naphthol (1 mmol), aldehyde (0.5 mmol), and activated
carbon sulfuric acid (0.03 g) as catalyst was heated at 80 °C. TLC evaluated the
reaction progress. After ending the reaction, the obtained mixture was rinsed with
ethyl acetate. Then, to separate and recover the catalyst, the mixture was ꢀltered.
Synthesize of 1,8‑dioxo‑octahydroxanthenes
The manner resembled that explained for synthesize 14-aryl-14H-
dibenzo[a,j]xanthenes with the exclusion that 2-naphthol was supplanted with
5
,5-dimethyl-1,3-cyclohexanedione.
Fig. 1 Preparation of ACSA
1
3

A. Marandi et al.
Results and discussion
Characterization of catalyst
FT‑IR analysis
The FT-IR spectra obtained from AC at diverse stages of manufacturing are shown
−1
−1
in Fig. 2. The 3436 cm and 1158 cm bands are assigned to the O–H stretch
band and the C–O stretch band, respectively, which proves hydroxyl (-OH) groups
on the AC surface in the pristine AC (Fig. 2a). The reason for the hydroxyl groups’
presence seems to the loading of atmospheric moisture on the surface or the oxida-
−
1
−1
tion of raw materials during reꢀning [49]. Other bands at 1639 cm , 1562 cm ,
−1
−1
1
384 cm , and 1406 cm are attributed to the C=O stretching vibration mode of
quinone groups, C=C stretching vibration mode of aromatic rings, C–O–H bend-
ing vibration mode, respectively. For the oxidized AC (Fig. 2b), two bands emerged
−1
−1
at 1717 cm and 1233 cm , ascribed to the C=O and C–O stretching vibrations
modes carboxylic groups, respectively. After oxidation, increasing hydroxyl groups
−
1
−1
has led to increased relative intensities of peaks at 1233 cm and 3425 cm . This
Fig. 2 FT-IR spectra of pristine (a), acid-treated (b), reduced (c), and sulfonized (d) ACs
1
3

Fabrication of activated carbon sulfuric acid as an excellent…
evidence conꢀrms that the surface of the AC is activated by acid treatment and
functionalized. Reduction of the COOH groups to OH groups in the reduced AC
−
1
(
Fig. 2c) conꢀrmed by the band’s vanish at 1715 cm and the advent of a band
−1
at 942 cm , allocated to the stretching vibration mode of C–O. The sulfonation
of AC (Fig. 2d) shows the O=S=O asymmetric and symmetric stretching bands at
−1
−1
−1
1
190–1220 cm and 1080–1109 cm , respectively, and a peak at 600–700 cm
that related to the S–O stretching mode. The spectrum also displays a broad OH
stretching band around 3700 cm− and 2800 cm .
1
−1
XRD analysis
XRD pattern of sample AC and its sulfonated derivative are depicted in Fig. 3, and
the identical peaks are perceived in both the pristine and sulfonic acid-anchored AC.
These results mean that the structure of the AC core is preserved within the sulfona-
tion process. The peaks in the XRD pattern corresponding to the Miller index value
ascribed to the amorphous carbon.
TGA/DGT analysis
The thermogravimetric analysis (TGA) and derivative thermogravimetry (DTG)
curve of the sulfonic acid functionalized AC are shown in Fig. 4. TGA and DGT
were used to determine the stability of the support layer on the catalyst. Two weight-
loss peaks in the temperature range of 120 °C and 250 °C can be seen in Fig. 4,
Fig. 3 XRD diꢁraction pattern of AC and ACSA
1
3

A. Marandi et al.
Fig. 4 TGA and DTG pattern for ACSA
which could be due to the removal of moisture adsorbed on the surface of the cata-
lyst and the degradation and removal of sulfonic acid groups, respectively.
XPS analysis
X-ray photoelectron spectroscopy (XPS) facilitates us to be aware of the presence
of elements inside the material or elements that cover the surface of the material.
XPS (C 1s) spectra for pristine AC, acid-treated AC, reduced AC, and sulfonated
AC are shown in Fig. 5. The C 1s peaks shown in the pristine AC (Fig. 5a) can be
converted to 285.0, 286.4, 287.8, 288.8, and 289.9 eV [50, 51]. The contribution of
plasmon at 291.0 eV was negligible. In the acid-treatment curve (Fig. 5b), the peaks
at around 288.1 and 289.6 eV are ascribed to the CO and COO groups, respectively.
These peaks depict 6.78% and 4.55% carbon signals larger and more signiꢀcant
than the pristine AC (Table 1). Due to the enhancement in atomic oxygen content
from 4.73% (pristine AC) to 14.03 % (acid-treated AC), it can be concluded that
the acid treatment process has been successful and has led to the creation of more
functional groups at the surface of AC (Table 2). After reduction, AC depicted the
identical pattern with the attendance of O 1s and C 1s peaks (Fig. 5c). The reduction
of carboxylic acid groups to alcoholic groups can be understood by decreasing the
acidic ingredient at 289.6 eV and increasing the alcoholic components at 287.2 eV
(
Table 1). AC sulfonate (Fig. 5d) depicts the same pattern as the reduced pattern,
except that a new peak (single S 2p) emerges at 168 eV corresponding to S–O with
1
3

Fabrication of activated carbon sulfuric acid as an excellent…
Fig. 5 C 1 s XPS spectrum of pristine (a), acid-treated (b), reduced (c), and solfunized (d) ACs
Table 1 Summary of the relative percentage of carbon and assignation
2
3
Binding energy (eV)
and assignation
C SP
285
C SP
C–O
–C=O
CO–O
286–286.4
287–287.2
288.48–288.69
289.3–289.9
Pristine
Acid-treated
Reduced
74.03
69.13
69.44
70.25
8.6
3.08
6.78
7.30
7.27
2.21
5.62
5.83
4.63
2.01
4.55
4.17
4.89
12.08
11.67
11.38
Sulfonized
Table 2 Summary of the
Element (Atom%)
C
O
S
element composition of the ACs
Pristine
Acid-treated
Reduced
95.27
85.97
86.06
75.76
4.73
14.03
13.94
63.8
–
–
–
Sulfonized
3.10
1
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A. Marandi et al.
an elemental percentage of 3.1%. Accordingly, after the sulfonation process, the cat-
alyst contains SO H groups, and all sulfur atoms exist in SO H groups [52]. Due to
3
3
the increase in the atomic percentage of oxygen in the sulfonated state (63.8%) com-
pared to the pristine state (4.37%), it is quite evident that the sulfonic groups were
immobilized on the AC.
Neutralization titration
Based on the neutralization titration results, the acidity of this catalyst is equal to
-
1
2
.385 mmol.g , which demonstrates that the fabricated catalyst acts as a robust solid
acid with a high density of acidic sites.
Catalytic activity
As a ꢀrst attempt to study the yield and reaction time, one equivalent of 2-naph-
thol and 0.5 equivalent of 4-chlorobenzaldehyde was examined at 80 °C under the
solvent-free conditions, and low yield (< 30%) was obtained after 9 h (Table 3,
Entry 1). In order to optimize the reaction and meliorate the product’s eꢂciency,
ACSA (0.2 g) was added, and the reaction was performed under the same condi-
tions. A remarkable betterment was observed in the reaction time and product yield
(
Table 3, Entry 2). With this promising result, more evaluations about the optimal
reaction conditions were performed, and the reaction was accomplished with diverse
amounts of catalysts. When the catalyst amount was reduced from 0.2 to 0.03 g,
the reaction time was improved from 45 to 20 min, and the product’s yield was
improved from 80 to 97% (Table 3). By further reducing the amount of catalyst to
0
8
0
.02, the eꢂciency even reached 97%, but suddenly the reaction time increased to
5 min (Table 3, Entry 5), so the optimal amount of catalyst for this reaction was
.03 g.
The next step after optimizing the amount of catalyst is to specify the application
range of the ACSA. An extensive range of aromatic aldehydes was exposed to react
with 2-naphthol in the attendance of the optimum amount of ACSA, at 80 °C under
the solvent-free conditions to produce corresponding 14-aryl-14H-dibenzo[a,j]xan-
thenes (Fig. 6). The results are summarized in Table 4. It is speciꢀed that various
Table 3 Inꢄuence of the amount
Yield (%)a
Entry
ACSA (g)
Time (min)
of ACSA on the synthesis
of 14-aryl-14H-dibenzo[a,j]
xanthenes
1
2
3
4
5
6
–
540
45
30
24
20
85
Trace
80
85
92
97
0.2
0.1
0.05
0.03
0.02
97
4
-chlorobenzaldehyde-2-naphthol=0.5:1, Solvent-free, 80 °C
a
Refers to isolated yields
1
3

Fabrication of activated carbon sulfuric acid as an excellent…
Fig. 6 Synthesis of 14-aryl-14H-dibenzo[a,j]xanthene catalyzed by ACSA
substitutions in the aryl group of aldehydes have not shown much impact on the
generation of the ultimate product and aꢁord the anticipated product in good yields.
The reaction of diverse aromatic aldehydes with 5,5-dimethyl-1,3-cyclohexanedi-
one instead of 2-naphthol was performed in solvent-free conditions at 80 °C caused
1
,8-dioxo-octahydroxanthene derivatives were created with excellent yield and after
a short time (Fig. 7, Table 5).
All products were separated by ꢀltration and were identiꢀed by spectroscopic
1
13
methods such as FT-IR, HNMR, CNMR, and CHN and compared with reference
data (Figures 1S–38S). Also, product 5g (Entry 8, Table 5) was adopted to deter-
mine the structure by X-ray single-crystal diꢁraction (Fig. 8).
Mechanism of reactions
Possible and acceptable mechanisms for 14-aryl-14H-dibenzo[a,j]xanthene and
1
,8-dioxo-octahydroxanthene synthesis are proposed in Schemes 1 and 2, respec-
tively. Both mechanisms are almost identical and generally involve a Knoevenagel
condensation, a Michael addition, and ꢀnally, a cyclocondensation reaction. Also,
the role of ACSA catalyst in these two mechanisms is similar: to enhance the car-
bonyl group’s electrophilicity by protonation and promote the addition of nucleo-
philes to the aldehyde. In the generation process of 14-aryl-14H-dibenzo[a,j]xan-
thene (Scheme 1), ꢀrst, due to the nucleophilic addition of a β-naphthol molecule
to an ACSA-activated aldehyde, intermediate I is formed, and then after dehydra-
tion, intermediate II is created (Knoevenagel condensation). The nucleophilic attack
of the second β-naphthol on the β-carbon of the existing α,β-unsaturated carbonyl
group in activated intermediate II results in the formation of intermediate III, which
ultimately desired product IV is generated by the conversion of intermediate III by a
cyclocondensation reaction.
The same is true of the 1,8-dioxo-octahydroxanthene synthesis mechanism.
For this purpose, the aldehyde ꢀrst is activated by the ACSA catalyst and attacked
by the dimedone molecule as the nucleophile, forming an intermediate I. Then,
by removing a molecule of water, the Knoevenagel condensation is completed,
and the intermediate of II is created. Another dimedone molecule then reacts
with intermediate II by Michael addition, resulting in produced intermediate III.
Finally, the conversion of intermediate III to the 1,8-dioxo-octahydroxanthene IV
1
3

A. Marandi et al.
a
Table 4 ACSA catalyzed synthesis of 14-aryl-14H-dibenzo[a,j]xanthene
b
Entry
Aromatic aldehyde
Product
Time (min) Yield (%)
1
30
95
4
a
2
3
40
92
4
b
20
70
97
93
4
c
4
4
d
c
5
6
7
17
30
10
94
90
98
4
e
4
f
4
g
c
8
9
50
92
89
4
h
21
4
i
1
0
1
100
20
87
94
4
j
1
4
k
1
3

Fabrication of activated carbon sulfuric acid as an excellent…
Table 4 (continued)
a
Some of the products were characterized by IR, H NMR, and 13C NMR spectroscopic data, CHN, and
1
melting points
b
Yields refer to isolated products
The reactants and catalyst were grinding thoroughly before heating
c
Fig. 7 Synthesis of 1,8-dioxo-octahydroxanthene catalyzed by ACSA
is done through the cyclocondensation reaction. In general, it can be declared that
the catalyst facilitates the formation of an intermediate of I in both reactions by
activating the aldehyde and enhancing the nucleophilic attack on it, improving
the rate of both reactions.
Catalytic activity comparison
In order to compare the catalytic activity of ACSA with other works for the syn-
thesis of 14-aryl-14H-dibenzo[a,j]xanthene and 1,8-dioxo-octahydroxanthene
compounds, a summary of the results was gathered in Tables 6 and 7, respectively.
Table 6 shows that the yield and time required for 14-phenyl-14H-dibenzo[a,j]
xanthene (4a) synthesis are lower than the other catalysts.
To compare the catalytic activity of the catalyst with other works, we adopted
product 5a as a representative of the 1,8-dioxo-octahydroxanthene, and the results
of this comparison are summarized in Table 7. As can be observed, the reaction
yield of this catalyst is better than other catalysts, and the reaction time is faster
than others.
Reusability of catalyst
Catalyst recycling is an essential issue for heterogeneous catalysts so that the cata-
lyst can be removed with a simple decanter, and after rinsing with acetone and air
drying without the need for any deactivation, it can be used ꢀve times (Table 8).
1
3

A. Marandi et al.
a
Table 5 ACSA catalyzed synthesis of 1,8-dioxo-octahydroxanthene
b
Entry
Aromatic aldehyde
Product
Time (min)
40
Yield (%)
1
97
5
a
2
3
60
55
95
5
b
95
5
c
c
5
6
7
30
90
91
92
5
d
40
20
5
e
5f
c
8
9
53
97
5
5
g
90
40
97
92
h
10
5
i
1
3

Fabrication of activated carbon sulfuric acid as an excellent…
Table 5 (continued)
a
Some of the products were characterized by IR, H NMR, and 13C NMR spectroscopic data, CHN, and
1
melting points
b
Yields refer to isolated products
The reactants and catalyst were grinding thoroughly before heating
c
Fig. 8 X-ray structure of 5 g
Conclusion
Based on the demands of industries for cost-eꢁective and green methods, recy-
cling and recovery of sulfuric acid are important issues in developed countries
and industries. This study is the ꢀrst, which illustrates the utilization of the acti-
vated carbon as a support for sulfuric acid and shows its application in the syn-
thesis of 14-aryl-14H-dibenzo[a,j]xanthenes and 1,8-dioxo-octahydroxanthenes.
Features that make the catalyst stand out are stability and high catalytic activ-
ity, easy and fast preparation method, and cost-eꢁectiveness. This catalyst was
conꢀrmed by FT-IR, XRD, TGA, XPS, and neutralization titration technique,
1
and product synthesis was authenticated with information of FT-IR, HNMR,
1
3
CNMR, and CHN spectroscopy. The functionalization of activated carbon by
hydroxyl groups also opens up new approaches to their modiꢀcation.
1
3

A. Marandi et al.
Scheme 1 Proposed mechanism for 14-aryl-14H-dibenzo[a,j]xanthene synthesis
1
3

Fabrication of activated carbon sulfuric acid as an excellent…
Scheme 2 Proposed mechanism for 1,8-dioxo-octahydroxanthene synthesis
Table 6 Comparison of ACSA with other works for 14-phenyl-14H-dibenzo[a,j]xanthene synthesis
Entry
Catalyst
Conditions
Time
Yield (%)
Ref
1
2
3
4
5
6
7
SBA-15/SO H
FeCl3
Sulfamic acid
Selectꢄuor™
Silica sulfuric acid
PPA/SiO2
Dichloroethane, 85 °C
Solvent-free, 100 °C
Solvent-free, 125 °C
Solvent-free, 125 °C
Solvent-free, 80 °C
Solvent-free, 120 °C
Solvent-free, 80 °C
24 h
10 h
8 h
8 h
45 min
30 min
30 min
95
91
93
93
89
90
95
[42]
[39]
[53]
[54]
[55]
[40]
This work
3
ACSA
Table 7 Comparison of ACSA with other works for the 1,8-dioxo-octahydroxanthene synthesis
Entry
Catalyst
Conditions
Time
Yield (%)
Ref
1
2
3
4
5
Nickel NPs@N-doped TiO2
SA@Sawdust
[Bmim]HSO4
Silica sulfuric acid
ACSA
EtOH, 80 °C, reꢄux
Ethanol/reꢄux
Solvent-free, 80 °C
Solvent-free, 80 °C
Solvent-free, 80 °C
2.5 h
50 min
3 h
1 h
40 min
85
92
85
97
97
[56]
[57]
[58]
[55]
This work
1
3

A. Marandi et al.
Table 8 Reusability of ACSA
in the synthesis of xanthenes
derivatives
Run
1
2
3
4
5
Yield (%)a
97
97
95
92
92
4
-chlorobenzaldehyde-2-naphthol=0.5:1, Solvent-free, 80 °C
a
Refer to isolated yields
Supplementary Information The online version contains supplementary material available at https://doi.
org/10.1007/s11164-021-04457-z.
Acknowledgments The authors sincerely acknowledge the Research Council of Semnan University for
supporting this work.
Funding Semnan University, Grant Recipient: Dr. Nadiya Koukabi, Associated Professor.
Availability of data and material The manuscript has data included as electronic supplementary material.
Declaration
Conꢀict of interest All authors are aware of the submission and agree to its publication, and have no
conꢄicts of interest.
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