P-Sulfonic acid calix[4]arene as an efficient and reusable catalyst for the synthesis of acridinediones and xanthenes

Article abstract of DOI:10.1007/s11164-015-2001-x

p-Sulfonic acid calix[4]arene has been found to be an efficient catalyst for the synthesis of acridinediones and xanthenes under mild conditions in excellent yields. The present approach offers the advantages of simple methodology, short reaction time, an

Full text of DOI:10.1007/s11164-015-2001-x

Res Chem Intermed
DOI 10.1007/s11164-015-2001-x
p-Sulfonic acid calix[4]arene as an efficient
and reusable catalyst for the synthesis of acridinediones
and xanthenes
Seyed Meysam Baghbanian1 Gonja Khanzad1
•
•
Seyed Mohammad Vahdat1 Hamed Tashakkorian
2
•
Received: 2 December 2014 / Accepted: 5 March 2015
Ó Springer Science+Business Media Dordrecht 2015
Abstract p-Sulfonic acid calix[4]arene has been found to be an efficient catalyst
for the synthesis of acridinediones and xanthenes under mild conditions in excellent
yields. The present approach offers the advantages of simple methodology, short
reaction time, and high yield.
Keywords p-Sulfonic acid calix[4]arene Á Organocatalyst Á Xanthenes Á
Acridinediones
Introduction
Multi-component reactions play an important role in combinatorial chemistry
because of their ability to synthesize small drug-like molecules with several degrees
of structural diversity. These one-pot reactions introduce the most efficient method
to the molecular diversity [1].
Acridine derivatives possess a wide range of pharmaceutical activities, including
antibacterial [2], antitumor [3], anticancer [4], fungicidal [5], and DNA-binding
properties [6].
Xanthene derivatives are very important heterocyclic compounds because of their
wide range of biological and pharmaceutical properties such as anti-inflammatory
[7], antibacterial [8], antiviral [9], photodynamic therapy [10], and antiviral [11].
Electronic supplementary material Theonlineversion of this article (doi:10.1007/s11164-015-2001-x)
contains supplementary material, which is available to authorized users.
&
Seyed Meysam Baghbanian
s.m.baghbanian@iauamol.ac.ir; s.baghbanian@gmail.com
1
2
Department of Chemistry, Ayatollah Amoli Branch, Islamic Azad University, 698, Amol, Iran
Cellular and Molecular Biology Research Center (CMBRC), Babol University of Medical
Sciences, Babol, Iran
123

S. M. Baghbanian et al.
Furthermore, these compounds can be used as fluorescent dyes [12], pH-sensitive
fluorescent materials for visualization of biomolecular assemblies [13], and also
utilized in laser technologies [14]. Well-known dyes having a xanthene nucleus are
rhodamine B and rhodamine 6G. Therefore, the synthesis of xanthenes is of great
importance. Consequently, several methods have been developed for the synthesis
of xanthene derivatives, which in general can be obtained by the condensation of
aryloxymagnesium halides with triethyl orthoformate [15], the cyclization of
polycyclic aryl triflate esters [16], and the reaction of dimedone or b-naphthol with
aldehydes [17–25]. However, many of these existing methodologies suffer from one
or more disadvantages, such as toxic metal ions and solvent, high cost, high catalyst
loading, corrosive reagents, large amounts of solid supports, and cumbersome work-
up procedures.
In continuation of our studies on the development of new catalysts and offering
novel methodology in organic synthesis [26–33], herein we studied its efficiency to
catalyze two types of organic transformations, including the preparation of xanthene
and acridinedione derivatives under relatively mild conditions. Interestingly, p-
sulfonic acid calix[4]arene efficiently catalyzed the above reactions under the
mentioned conditions to give the desired products in high to excellent yields and in
relatively short reaction times (Scheme 1).
R1
O
O
O
O
O
R1
R= SO3H
R
Catalyst:
R
R
O
H
R
OH
Catalyst
R1
HO
OH
OH
OH
O
R1: H, Cl, Br, NO2, CH3
OCH3, OH
R1
R1
O
O
O
O
O
O
or
NH2
or NH4OAc
N
N
H
R2
R2: H, CH3, OCH3
R2
Scheme 1 The synthesis of xanthene and acridinedione derivatives in the presence of p-sulfonic acid
calix[4]arene as catalyst
123

p-Sulfonic acid calix[4]arene as an efficient and reusable…
Experimental
All reagents were prepared from analytical reagent-grade chemicals unless specified
otherwise and purchased from Merck. Melting points were measured with an
Electrothermal 9100 apparatus. Samples were analyzed using FT-IR spectroscopy
1
(using a Perkin-Elmer 65 in KBr matrix in the range of 4000–400 cm-1). H, 13C
NMR spectra were recorded on a BRUKER DRX-400 AVANCE spectrometer
using tetramethylsilane as an internal standard.
General procedure
First, p-tert-butylcalix[4]arene was prepared by the Gutsche and Iqbal method [34].
Secondly, the p-tert-butylcalix[4]arene was dealkylated by treatment with alumini-
um chloride in the presence of toluene and phenol according to the method
described by Ungaro et al. [35]. Preparation of p-sulfonic acid calix[4]arene was
carried out with the treatment of calix[4]arene with concentrated sulfuric acid
(98 wt%) added to the reaction mixture was shaken under nitrogen at 80 °C [36]
(Scheme 2).
General procedure for the synthesis of 25,26,27,28-tetrahydroxycalix[4]arene
A hot solution of p-tert-butylcalix[4]arene (5 g, 6.15 mmol) of toluene (250 ml)
was placed in a 500-ml, three-necked, round-bottomed flask fitted with a gas inlet
tube and a magnetic stirring bar. The temperature of the solution was reduced to
50 °C and then the anhydrous AlCl3 (5 g, 37 mmol) was added to this mixture
slowly under inert atmosphere conditions. After cooling in an ice bath, 125 ml of
1N HCl for 30 min was added, and the organic layer was separated and evaporated
to leave a yellow residue. Ether (500 ml) was added to the reaction mixture and the
precipitate was recrystallized from CHC13–CH3OH to yield white crystals, mp
312–316 °C.
General procedure for the synthesis of p-sulfonic acid calix[4]arene
Calix[4]arene (1.0 g, 2.4 mmol) was mixed with concentrated H2SO4 (10 ml) and
the solution was heated at 80 °C for 4 h. An aliquot was withdrawn from the
reaction mixture and poured into water. The reaction was completed when no water-
insoluble material was detected in the aliquot. After cooling, the precipitate was
filtered off through a glass filter. The residue was dissolved in hot water (15 ml) and
HO3S
SO3H
SO3H
HO3S
H2SO4
AlCl3
80 °C, 5 h
50 °C, 1N HCl
HO
HO
OH
OH
OH
OH
OH
HO
OH
OH
OH
OH
Scheme 2 Sulfonation of calix[4]arne using Shinkai method
123

S. M. Baghbanian et al.
the solution was adjusted to pH = 8 by Na2CO3. After filtration, methanol was
added to the filtrate to afford a white precipitate.
General procedure for the preparation of xanthene derivatives
A mixture of b-naphthol or dimedone (2 mmol), aldehydes (1 mmol), and
p-sulfonic acid calix[4]arene (1.5 mol%, 0.012 g) were added to 5 ml of ethanol
and the mixture was stirred in a round-bottomed flask at 80 °C for an appropriate
time. After completion of the reaction confirmed by TLC (thin-layer chromatog-
raphy) analysis (eluent: hexane/ethyl acetate 2:1), the mixture was cooled to room
temperature and the precipitated product was filtered and recrystallized from
ethanol. Finally, on filtration, ethanol was evaporated and the organocatalyst dried
and reused in successive reactions.
Spectroscopic data for selected examples are listed as follows:
14-(4-Chlorophenyl)-14H-dibenzo [a,j] xanthene (3b) Yellow solid; M.P.
284–286 °C (lit. 289–290 °C); IR (KBr) t 3155, 2968, 1648, 1558, 1528, 1496,
1383, 1265, 1247, 1219, 1150 cm-1. 1H NMR (400 MHz, CDCl3): d (ppm) = 6.49
(s, 1H), 7.13 (d, J = 8.4 Hz, 2H), 7.43–7.87 (m, 10H), 8.34 (d, J = 8.4 Hz, 2H),
8.66 (d, J = 7.6 Hz, 2H) ppm; 13C NMR (100 MHz, CDCl3): d (ppm) = 37.4,
116.7, 118.0, 122.4, 124.4, 126.9, 128.6, 128.9, 129.1, 129.5, 131.0, 131.2, 132.1,
143.5, 148.7 ppm.
9-(4-chlorophenyl)-3,3,6,6-tetramethyl-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-
dione (5b) White solid; M.P. 228–230 °C (lit. 230–232 °C); IR (KBr) t 2954, 1664,
1364, 1199 cm-1. 1H NMR (400 MHz, CDCl3): d (ppm) = 1.01 (s, 6H), 1.12 (s, 6H),
2.16–2.28 (dd, J = 16.4 Hz, 4H), 2.43–2.53 (m, 4H), 4.73 (s, 1H), 7.20 (d,
J = 8.4 Hz, 1H), 7.26 (d, J = 8.8 Hz, 2H) ppm; 13C NMR (100 MHz, CDCl3):
d = 27.3, 29.3, 32.2, 40.8, 50.7, 115.3, 128.2, 129.8, 132.0, 142.7, 162.4, 196.4 ppm.
General procedure for the preparation of acridine derivatives
A mixture of dimedone (2 mmol), aldehydes (1 mmol), aromatic amine or
ammonium acetate (1.2 mmol), and p-sulfonic acid calix[4]arene (1.5 mol%,
0.012 g) were added to 5 ml of ethanol and the mixture was stirred in a round-
bottomed flask at 80 °C for an appropriate time. After completion of the reaction
confirmed by TLC (eluent: hexane/ethyl acetate 2:1), the mixture was cooled to
room temperature and the precipitated product was filtered and recrystallized from
ethanol. Finally, on filtration, ethanol was evaporated and the organocatalyst dried
and reused in successive reactions.
9-(4-Chlorophenyl)-10-(4-methoxyphenyl)-3,3,6,6-tetramethyl-3,4,6,7,9,10-hexahy-
droacridine-1,8(2H,5H)-dione (7h) White solid; mp 270–272 °C (lit.
270–271 °C); IR (KBr) t 2956, 1592, 1490, 1373, 1259 cm-1
.
1H NMR
(400 MHz, CDCl3): d = 1.01 and 1.12 (2s, 12H), 2.16–2.28 (m, 4H), 2.48 (s,
4H), 3.86 (s, 3H), 4.73 (s, 1H), 6.95 (d, J = 8.5 Hz, 2H), 7.25 (d, J = 8.4 Hz, 2H),
7.45 (t, J = 7.4 Hz, 4H), 7.84 (t, J = 7.4 Hz, 4H) ppm; 13C NMR (100 MHz,
123

p-Sulfonic acid calix[4]arene as an efficient and reusable…
CDCl3): d = 27.5, 29.4, 31.2, 32.3, 40.9, 50.9, 55.2, 113.5, 115.8, 121.3, 123.4,
129.5, 129.8, 136.6, 158.4, 163.1, 168.6, 196.6 ppm.
9-(4-methoxyphenyl)-3,3,6,6-tetramethyl-3,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-
dione (7m) White solid; mp 271–274 °C (lit. 270–272 °C); IR (KBr) t 3214, 2978,
1658, 1642, 1496, 1265 cm-1; 1H NMR (400 MHz, CDCl3): d = 1.05 and 1.09 (2S,
12H), 2.16–2.38 (m, 8H), 3.72 (S, 3H), 5.22 (S, 1H), 6.78 (d, J = 8.8 Hz, 2H), 7.39 (d,
J = 8.8 Hz, 2H), 8.18 (S, 1H) ppm; 13C NMR (100 MHz, CDCl3): d = 27.2, 30.1,
31.3, 40.3, 51.4, 55.6, 112.9, 114.3, 129.8, 136.7, 149.7, 157.4, 195.4 ppm.
Results and discussion
The calixarenes are a class of cyclooligomers formed via a p-substituted phenols
and formaldehyde condensation. p-Sulfonic acid calix[4]arene has shown some
interesting capabilities in preparation of conducting polymer, polyaniline, as a
doping agent [37], encapsulating to topotecan for improving solubility in
chemotherapy [38], and has bee proven to be suitable for bio-pharmaceutical
applications [39].
The p-sulfonic acid calixarenes have been reported as catalysts in Mannich-type
reactions [40], allylic alkylation reactions [41], and esterification reactions [42].
This catalyst offers several advantages including shorter reaction times, mild
reaction conditions, cleaner reactions, lower catalyst loading, and simple ex-
perimental procedures with high yields.
Study of the efficacy of p-sulfonic acid calix[4]arene in the synthesis of 14-
aryl-14H-dibenzo[a,j]xanthenes and 1,8-dioxo-octahydroxanthenes
To find the optimized condition for the synthesis of this class of compounds, the
reaction of benzaldehyde (1 mmol) with b-naphthol (2 mmol) as a model reaction
in the presence of different amounts of p-sulfonic acid calix[4]arene, was examined
(Scheme 3) and variables affecting on the reaction yields were studied. The
optimum amount of p-sulfonic acid calix[4]arene was 1.5 mol% as shown in
Table 1, entry 8. The influence of solvent was studied when the model reaction was
performed using p-sulfonic acid calix[4]arene under various solvents and solvent-
free conditions (Table 1). As can be seen in Table 1, ethanol was found to be a
suitable solvent in the presence of 1.5 mol% of the catalyst (Table 1, entry 8).
Next, we examined the scope of the reaction by using various aromatic aldehydes
and the results are summarized in Table 2. In all cases, the corresponding xanthene
derivatives were obtained in good to excellent yields. The reaction of b-naphthol
and aldehydes in the presence of p-sulfonic acid calix[4]arene (1.5 mol%, 0.012 g)
as an organocatalyst under optimized conditions yielded desired 14-aryl-14H-
dibenzo[a,j]xanthenes in excellent yields (Table 2, entries 1–10). The reactions of
aromatic aldehydes having electron withdrawing groups were somewhat faster than
electron donating groups (Table 2, entries 2–7). Though meta- and para- substituted
123

S. M. Baghbanian et al.
R
R
R
R
Catalyst =
HO
OH OH
OH
R= SO3H
CHO
OH
1.5 mol % Catalyst
EtOH, 80 °C
2
O
3a
1
2
Scheme 3 The model reaction for the synthesis of dibenzo[a,j]xanthene 3a
Table 1 Optimization of reaction conditions for synthesis of compound 3
Entry
Catalyst (mol%)
Solvent
Temp. (°C)
Time (h)
Yield (%)a
1
0.5
0.5
0.5
0.5
0.5
1.5
1.5
1.5
0.5
0.5
0.5
0.5
1
CH3CN
CH2Cl2
EtOH
r.t.
r.t.
r.t.
50
80
r.t.
50
80
r.t.
80
r.t.
80
80
2
50
40
60
75
85
75
80
98
30
70
30
45
70
2
2
3
2
4
EtOH
2
5
EtOH
2
6
EtOH
2
7
EtOH
1
8
EtOH
45 (min)
9
H2O
2
2
1
1
1
10
11
12
13
H2O
Solvent-free
Solvent-free
Solvent-free
Reaction condition: benzaldehyde (1 mmol), b-naphthol (2 mmol), p-sulfonic acid calix[4]arene
a
Isolated yield
aromatic aldehydes gave good results, ortho-substituted aromatic aldehydes gave
lower yields because of the steric effects (Table 2, entries 3 and 6).
After the successful application of p-sulfonic acid calix[4]arene in the synthesis
of 14-aryl-14H-dibenzo[a,j]xanthenes, we examined its efficacy in the preparation
of 1,8-dioxo-octahydroxanthenes.
For the initial study, as a model, the condensation of dimedone (2 mmol) and
benzaldehyde (1 mmol) was examined (Scheme 4) in the presence of different
molar ratios of p-sulfonic acid calix[4]arene in ethanol at various temperatures
ranging from 25 to 80 °C (Table 2, entries 1–6), which demonstrated 80 °C to be
the optimum temperature (Table 2, entry 6). The model reaction was also performed
in other solvents such as CH3CN, H2O, and CH2Cl2 instead of EtOH and solvent-
free conditions (Table 2, entries 7–10). Changing the solvent showed no further
increase in the yield under optimized conditions. Therefore, the best results were
123

p-Sulfonic acid calix[4]arene as an efficient and reusable…
Table 2 Optimization of reaction conditions for synthesis of compound 5
Entry
Catalyst (mol%)
Solvent
Temp. (°C)
Time (h)
Yield (%)a
1
2
0.5
0.5
0.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
EtOH
r.t.
50
80
r.t.
50
80
80
80
80
80
2
55
70
85
75
85
97
60
40
75
80
EtOH
2
3
EtOH
2
4
EtOH
2
5
EtOH
1
6
EtOH
35 (min)
7
CH3CN
CH2Cl2
H2O
1
1
1
1
8
9
10
Solvent-free
Reaction condition: benzaldehyde (1 mmol), dimedone (2 mmol), p-sulfonic acid calix[4]arene
a
Isolated yield
O
O
CHO
O
2
O
Catalyst
EtOH
O
1
5a
4
Scheme 4 The model reaction for the synthesis of 1,8-dioxo-octahydroxanthene 5a
obtained from the reaction of these components in EtOH in the presence of
1.5 mol % of the catalyst at 80 °C affording the 1,8-dioxo-octahydroxanthene 5a in
97 % yield within 35 min (Table 2, entry 6).
Under optimized reaction conditions, different aromatic aldehydes (such as
aldehydes bearing electron-withdrawing substituents, electron-releasing sub-
stituents, and halogens on their aromatic ring) were reacted with dimedone to
furnish the corresponding products in high yields and in short reaction times
(Table 3, entries 11–20). The aliphatic aldehyde underwent the reaction cleanly in
excellent yield (Table 3, entry 20).
Study of the efficacy of p-sulfonic acid calix[4]arene in the synthesis
of 1,8-dioxo-decahydroacridines
Considering the high importance of acridine derivatives, in the next step, we
examined the efficiency of p-sulfonic acid calix[4]arene in the synthesis of 1,8-
dioxo-decahydroacridines. To obtain the optimized reaction conditions for the
synthesis of this class of compounds, the reaction dimedone (2 mmol), benzalde-
hyde (1 mmol), and aniline (1.2 mmol) was selected as a model reaction
(Scheme 5). The effect of different molar ratios of p-sulfonic acid calix[4]arene,
123

S. M. Baghbanian et al.
Table 3 Synthesis of 14-aryl-14H-dibenzo[a,j]xanthenes and 1,8-dioxo-octahydroxanthenes in the
presence of p-sulfonic acid calix[4]arenes
Time
(min)
Yieldb
(%)
Entry
1
Aldehyde
CHO
Producta
M.p. °C (Lit.) [Ref.]
186–188
(184–185) [22]
45
98
O
(3a)
Cl
CHO
284-286
2
3
4
35
95
(289–290) [23]
Cl
O
(3b)
Cl
CHO
Cl
209-211
(214–216) [23]
45
35
92
95
O
(3c)
Br
CHO
294-297
(297–298) [17]
Br
O
(3d)
NO2
CHO
310-313
5
6
30
35
97
95
(311–312) [17]
O2N
O
(3e)
O2N
CHO
NO2
212-215
(214–215) [22]
O
(3f)
NO2
O2N
CHO
7
8
30
50
95
95
212–214
(213) [24]
O
(3g)
CH3
CHO
224–227
(227-229) [22]
H3C
O
(3h)
123

p-Sulfonic acid calix[4]arene as an efficient and reusable…
Table 3 continued
Time
Yieldb
(%)
Entry
9
Aldehyde
Producta
OCH3
M.p. °C (Lit.) [Ref.]
(min)
CHO
50
92
202-204
(203–205) [23]
H3CO
O
(3i)
OCH3
CHO
OCH3
179-182
10
11
45
35
92
97
(179–180) [17]
O
(3j)
O
O
CHO
199-201
(201–203) [43]
O
(5a)
Cl
O
O
CHO
228-230
12
13
14
40
45
15
95
88
98
(230-232) [43]
Cl
O
(5b)
Cl
O
O
CHO
Cl
223-226
(226–227) [18]
O
(5c)
NO2
O
O
CHO
227-229
(228–230) [19]
O2N
O
(5d)
NO
2
O
O
CHO
NO2
165-167
15
16
25
42
92
92
(168–170) [20]
O
(5e)
O
CH3
CHO
O
O
244-246
(248–250) [19]
O
H3C
O
(5f)
123

S. M. Baghbanian et al.
Table 3 continued
Time
(min)
Yieldb
(%)
Entry
Aldehyde
Producta
M.p. °C (Lit.) [Ref.]
CH3
O
O
CHO
218-220
17
35
40
95
90
(219–221) [43]
H3C
O
(5g)
OH
O
O
CHO
248-250
(249-251) [21]
18
HO
Br
O
(5h)
Br
OH
O
O
CHO
OH
248-252
19
20
50
60
85
88
(250–252) [25]
O
(5i)
H
O
3
C
CH
3
O
H3C
H3C
142-145
(146-147) [21]
CHO
O
(5j)
a
All compounds are known and their structures were established from their spectral data and melting
points as compared with literature values
b
The yields refer to isolated products
solvent, and temperature on the reaction was studied (Table 4). In order to optimize
the reaction conditions, the model reaction was performed in various solvents such
as H2O, CH3CN, EtOH, and CH2Cl2 (Table 4, entries 1–9). It was found that H2O,
CH3CN, CH2Cl2, and the solvent-free system were unfavorable for the formation of
the product 7a (Table 4, entries 7–10). The results indicated that higher yield of the
product and shorter reaction time were obtained when the reaction was carried out
using 1.5 mol% of the catalyst in ethanol at 80 °C (Table 4, entry 6).
Under optimized reaction conditions, dimedone with different aromatic aldehy-
des and aromatic amines or ammonium acetate were reacted to furnish the
corresponding 1,8-dioxo-9-aryl-decahydroacridines in good yields in the presence
of 1.5 mol% p-sulfonic acid calix[4]arene (Table 5). Aromatic aldehydes containing
electron-withdrawing groups (such as nitro, halide groups) or electron-donating
groups (alkyl, hydroxyl and alkoxyl groups) were employed and the nature of
substituents on the aromatic ring of the aldehydes did not show estimated strong
123

p-Sulfonic acid calix[4]arene as an efficient and reusable…
H
O
O
O
O
NH2
Catalyst
2
EtOH, 80 °C
O
N
6
4
1
7a
Scheme 5 The model reaction for the synthesis of 1,8-dioxo-decahydroacridine 7a
Table 4 Optimization of reaction conditions for synthesis of compound 7a
Entry
Catalyst (mol%)
Solvent
Temp. (°C)
Time (h)
Yield (%)a
1
2
0.5
0.5
0.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
EtOH
r.t.
50
80
r.t.
50
80
80
80
80
80
1
40
60
75
85
90
95
75
55
85
75
EtOH
1
3
EtOH
1
4
EtOH
1
5
EtOH
1
6
EtOH
30 (min)
7
CH3CN
CH2Cl2
H2O
1
1
1
1
8
9
10
Solvent-free
Reaction condition: benzaldehyde (1 mmol), dimedone (2 mmol), and aniline (1.2 mmol), p-sulfonic acid
calix[4]arene
a
Isolated yield
effects in terms of yields under these reaction conditions. We also observed that
ammonium acetate and various aromatic amines reacted easily under the conditions.
The use of anilines as the ammonium source afforded the desired product in lower
yield than ammonium acetate as the ammonium source. The reason may be that
ammonia released from ammonium acetate is more nucleophilic than aromatic
amines like aniline.
The reaction was clean and the products were obtained in high yields without the
formation of any by-products. All the xanthene and acridine derivatives prepared
were known compounds and their structures were confirmed by their physical
1
properties and H and 13C NMR spectra and comparison with authentic samples.
The catalyst was simply recovered from the reaction mixture by treating the
precipitate with ethanol to dissolve the catalyst. Finally, on filtration, ethanol was
evaporated and the organocatalyst dried and reused in successive reactions. The
recycled catalyst was found to be highly efficient even after six times without any
significant loss of catalytic activity.
123

S. M. Baghbanian et al.
Table 5 Synthesis of 1,8-dioxo-decahydroacridines catalyzed by p-sulfonic acid calix[4]arene
Time
(min)
Yieldb
(%)
Entry
Aldehyde
Amine
Producta
M.p. °C (Lit.) [Ref.]
O
O
O
H
NH2
255-256
1
30
40
95
85
N
(254-256) [44]
7a
CH3
O
H
O
O
NH2
261-263
(260-263) [45]
2
N
CH3
7b
NO2
O
H
O
O
NH2
290-292
3
4
20
25
92
85
(289-290) [45]
N
NO2
7c
NO2
O
O
H
O
NH2
297-298
(297-299) [44]
N
NO2
7d
Cl
O
H
O
O
NH2
245-247
5
6
20
40
95
85
(244-246) [44]
N
Cl
7e
OCH3
O
H
NH2
O
O
219-222
(220-222) [44]
N
OCH3
7f
123

p-Sulfonic acid calix[4]arene as an efficient and reusable…
Table 5 continued
Time
(min)
Yieldb
(%)
Entry
Aldehyde
Amine
Producta
M.p. °C (Lit.) [Ref.]
O
O
NH2
CH3
O
H
261-263
N
7
25
17
25
90
95
90
(260-263) [46]
CH3
7g
Cl
O
H
O
O
NH2
CH3
270-272
(270-271) [46]
8
9
N
Cl
CH3
7h
O
O
NH2
O
H
216-217
(215-217) [47]
N
OCH3
OCH3
7i
CH3
O
H
O
O
NH2
240-241
(238-240) [46]
10
35
85
N
CH3
OCH3
OCH3
7j
O
O
O
H
H
278-279
11
12
NH4OAc
NH4OAc
20
15
95
95
(272-273) [48]
N
H
7k
Cl
O
O
O
303-304
(300-302) [49]
N
H
Cl
7l
123

S. M. Baghbanian et al.
Table 5 continued
Time
(min)
Yieldb
(%)
Entry
Aldehyde
Amine
Producta
M.p. °C (Lit.) [Ref.]
OCH3
O
H
O
O
271-274
(270-272) [50]
13
NH4OAc
20
90
N
H
OCH3
7m
CH3
O
H
O
O
318-320
14
15
NH4OAc
NH4OAc
25
15
85
95
(298-309) [51]
CH3
N
H
7n
NO2
O
H
O
O
322-324
(300) [52]
N
H
NO2
7o
a
All compounds are known and their structures were established from their spectral data and melting
points as compared with literature values
b
The yields refer to isolated products
Conclusions
In this study, a simple, efficient, and eco-friendly procedure is described for the
synthesis of 14-aryl-14H-dibenzo[a,j]xanthenes, 1,8-dioxo-octahydroxanthene and
1,8-dioxo-decahydroacridine derivatives in ethanol and under mild conditions using
p-sulfonic acid calix[4]arene as a reusable organocatalyst. The present approach
offers the advantages of simple methodology, clean and mild reaction conditions,
short reaction time, low loading of catalyst, high yield, and excellent product purity.
Acknowledgments This research was supported by the Islamic Azad University, Ayatollah Amoli
Branch, I. R. Iran.
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