A novel polymeric catalyst for the one-pot synthesis of xanthene derivatives under solvent-free conditions

Article abstract of DOI:10.1007/s13738-012-0092-5

A simple, efficient, and environmentally benign route was developed for the preparation of 14-aryl or alkyl- 14H-dibenzo[a,j]xanthene, 1,8-dioxo- octahydroxanthene and 12-aryl-8,9,10,12-tetrahydrobenzo[a]xanthene-11-ones from condensation of various aldeh

Full text of DOI:10.1007/s13738-012-0092-5

J IRAN CHEM SOC (2012) 9:757–765
DOI 10.1007/s13738-012-0092-5
ORIGINAL PAPER
A novel polymeric catalyst for the one-pot synthesis of xanthene
derivatives under solvent-free conditions
•
Behrooz Maleki Shahram Barzegar
•
•
•
Zeinalabedin Sepehr Mina Kermanian
Reza Tayebee
Received: 18 February 2011 / Accepted: 21 February 2012 / Published online: 22 May 2012
Ó Iranian Chemical Society 2012
Abstract A simple, efficient, and environmentally benign
route was developed for the preparation of 14-aryl or alkyl-
14H-dibenzo[a,j]xanthene, 1,8-dioxo-octahydroxanthene
and 12-aryl—8,9,10,12-tetrahydrobenzo[a]xanthene-11-ones
from condensation of various aldehydes with (i) b-naphthol,
(ii) cyclic 1,3-dicarbonyl compounds and (iii) b-naphthol
and cyclic 1,3-dicarbonyl compounds, using novel poly-
meric catalyst [poly(AMPS-co-AA)] under solvent-free
conditions. Use of easily available catalyst, shorter reaction
times, better yields, simplicity of the reaction, hetero-
geneous system, and easy work-up are the advantages of
the present method.
as dyes [8] and antagonists for the paralyzing action of
zoxazolamine [9]. Xanthenedione derivatives are valuable
synthons because of the inherent reactivity of the inbuilt
pyran ring [10]. They are also found as core units in several
natural products [11].
Polymer-supported reagents have been in use since
1946, and have been the subject of many review articles
[12, 13]. Synthesis using these reagents is attractive and
suitable for parallel synthesis because the reactions often
proceed with high yields, and the work-up involves simple
filtration and evaporation of the solvent. Polymeric
reagents can also be used in flow systems [14]. Moreover,
the reactions using polymer-supported reagents were car-
ried out with the reagents in ‘‘T-bags’’ so that when each
particular reaction was completed the ‘‘T-bag’’ was simply
removed and washed [15]. Therefore, it is reasonable to
assume that polymeric reagents will be employed with
increasing regularity to conduct one to multistage synthetic
sequences. To facilitate this mentioned use, the technique
requires rapid development, particularly in the following
areas: (i) the search for new functionalized polymers, and
(ii) the development of new solid supports with properties
specifically optimized for the synthetic procedure. Two
approaches exist for the preparation of functional poly-
mers, the polymerization or copolymerization of monomers
which carry out the desired functionality, and the chemical
modification of performed polymers. With these assump-
tions, during the course of systematic study on the devel-
opment of supported reagents and catalysts for the organic
transformation [16], we decided to investigate poly(2-ac-
rylamido-2-methyl propane sulphonic acid) (AMPS)
crosslinked with N,N0-methylene bisacrylamide (MBA) as
a novel catalyst for the synthesis of xanthene derivatives.
Because of their wide range of pharmacological activity
and also their industrial and synthetic applications, several
Keywords b-Naphthol ꢀ Aldehydes ꢀ Poly(AMPS-co-AA) ꢀ
Cyclic 1 ꢀ 3-Dicarbonyl compounds ꢀ Solvent-free
Introduction
Xanthene and benzoxanthene have attracted considerable
interests because of their wide range of antibacterial,
antiviral and anti-inflammatory activities as well as
phototoxicity and antagonist activity [1–3]. Some xanthene
derivatives are used in industry, such as PH sensitive flo-
rescent material for the visualization of biomolecular
assemblies [4, 5], in laser technologies due to their useful
spectroscopic properties [6], in photodynamic therapy [7],
B. Maleki (&) ꢀ Z. Sepehr ꢀ M. Kermanian ꢀ R. Tayebee
Department of Chemistry, Hakim Sabzevari University,
PO Box 397, Sabzevar, Iran
e-mail: maleki@sttu.ac.ir
S. Barzegar
Basic Science Department, Jundi Shapur University
of Technology, Dezful, Iran
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J IRAN CHEM SOC (2012) 9:757–765
methods have been reported for the synthesis of xanthene
and benzoxanthene, which include trapping of benzynes by
phenols [17, 18], cyclodehydration [19], cyclocondensation
between 2-hydroxyaromatic aldehydes and 2-tetralone
[20], and intramolecular phenyl carbonyl coupling reac-
tions of benzaldehyde and acetophenones [21]. Also,
14-aryl or alkyl-14H-dibenzo [a,j]xanthene and related
products have been prepared by the reaction of b-naphthol
with formamide [22], 2-naphthol-1-methanol [23] and
carbon monoxide [24]. Among these methods, the con-
densation reaction of aldehydes with (i) b-naphthol (ii)
cyclic 1,3-dicarbonyl compounds and (iii) b-naphthol and
cyclic 1,3-dicarbonyl compounds is one of the most simple
and straightforward approaches for the synthesis of 14-aryl
or alkyl-14H-dibenzo[a,j]xanthene, 1,8-dioxo-octahydrox-
anthene and 12-aryl—8,9,10,12-tetrahydrobenzo[a]xan-
thene-11-ones, respectively. A variety of reagents such as
P2O5/Al2O3 under microwave irradiation [25], silica sul-
furic acid [26, 27], boric acid [28], BF3.SiO2 [29], oxalic
acid [30], TaCl5 [31], KAl(SO4)2.12H2O (alum) [32], tet-
rabutylammonium bromide [33], 1-methyl-3-propane-imi-
dazolium hydrosulfate [34], methanesulfonic acid [35],
ZrOCl2.8H2O [36], polyaniline-p-toluenesulfonate salt
[37], antimony trichloride. SiO2 [38], trichloroisocyanuric
acid [39], NaHSO4.SiO2 [40], p-TSA in ionic liquid
([bmim]BF4) [41], InCl3 or P2O5 [42, 43], strondium tri-
flate [44], praline triflate [45], HBF4.SiO2 [46], 1-butyl-3-
methylimidazolium hydrogen sulfate [bmim]HSO4 [47],
cellulose sulfuric acid [48], HClO4.SiO2 [49],
H14[NaP5W30O110] [50], cyanuric chloride [51, 52], Caros
acid [53], nano-TiO2 [54], and selectfluorTM [1-(chloro-
methyl)-4-fluoro-1,4-diazoniabicyclo[2,2,2]octane bis(tet-
rafluoroborate) [55] have been employed to accomplish
this transformation. Each of these methods involves the use
of violent reaction conditions, long reaction times and
tedious procedures which afford the product in poor yields.
Thus, there is a certain need for the development of an
alternative for the production of xanthene derivatives,
which surpasses those limitations.
Experimental
IR spectra were recorded on a Shimadzu 435-U-04 spec-
trophotometer (KBr pellets). 1H NMR spectra were obtained
using Jeol FT NMR 90 MHz spectrometer in CDCl3 using
TMS as an internal reference. Melting points were deter-
mined in open capillary tubes in a Stuart BI Branstead
Electrothermal Cat No:IA9200 apparatus and uncorrected.
Synthesis of crosslinked poly(AMPS-co-AA)
N,N0-methylene bisacrylamide (MBA, 2 g) as a crosslinker
was added to the mixture of 2-acrylamido-2-methylpro-
pane sulphonic acid (AMPS 10 g) and acrylic acid (AA
10 mL) in 100 ml distilled water. The solution was added
to a three-neck reactor equipped with a mechanical stirrer
(Heidolph RZR 2021, three blade propeller type). The
reactor was immersed in a thermostated water bath at
70 °C. An inert gas (nitrogen) was gently bubbled into the
reactor to remove the oxygen. After 15 min, the ammo-
nium persulphate solution (APS 0.2 g in 2 mL H2O) was
added to the mixture, and the mixture was allowed to stir
(200 rpm) for 20 min. To remove probably unreacted
monomer, 1 g of polymer was added to excess distilled
water and the mixture allowed to stir gently for 72 h. Then,
the polymer was filtered and poured to excess methanol
and remained for 48 h. Then, methanol was decanted and
the product divided into small pieces. Finally, the polymer
was dried in oven. After grinding, the powdered polymer
was kept away from moisture, heat and light. The IR
spectrum of the polymer showed the characteristic
absorption of acid (O–H) groups at 3,444 cm-1, carbonyl
groups at 1,654 cm-1 and R2CH2-SO32 (AMPS) at
1,206 cm-1 (Fig. 1).
Instrumental analysis
A simultaneous thermal analyzer (STA-625, Geometric
Scientific) was used for thermo gravimetric analysis of
SO3H
COOH
H
H
H
N
N
N
N2 atmosphere
70°C
COOH
+
+
SO3H
COOH
SO3H
O
O
m
n
O
O
l
Crosslinked Poly AMPS-co-AA
Fig. 1 The synthesis of crosslinked poly(AMPS-co-AA)
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J IRAN CHEM SOC (2012) 9:757–765
759
Synthesis of 1,8-dioxo-octahydroxanthene
AA-co-AMPS polymer under nitrogen atmosphere. The
heating rate was 20 °C/min. The sample weight taken for
TG was 10.0 mg.
To a mixture of b-naphthol (2, 1 mmol) and cyclic 1,3-
dicarbonyl compounds (4, 2 mmol), crosslinked poly
(AMPS-co-AA) (0.04 g) was added and the mixture was
heated on an oil bath at 110 °C for the reasonable time.
After completion of the reaction, hot ethanol was added to
the mixture and then filtered. The residue was recrystal-
lized from ethanol. The results obtained are showed in
Table 3.
Thermal characterization
Thermal data obtained from TGA and DTGA traces are
included in Fig. 2. The copolymer exhibits three distinct
weight losses in its thermo gravimetric curve. The first one
is in the range of 38–181 °C attributed to loss of water
(9.3 wt%), and the two others are in the range of
183–335 °C with maximum decomposition rate at 297 °C
(weight loss 47 %) and 187–496 °C with maximum
decomposition rate at 416 °C (weight loss 82 %).
Synthesis of 12-aryl-8,9,10,12-
tetrahydrobenzo[a]xanthene-11-ones
In a separate set of experiments, to a mixture of b-naphthol
(2, 1 mmol), cyclic 1,3-dicarbonyl compounds (4,
1.2 mmol), and aldehyde (1, 1 mmol), crosslinked poly
(AMPS-co-AA) (0.06 g) was added and the mixture was
heated on an oil bath at 110 °C for the reasonable time and
these reactions were all repeated exactly under the above
same conditions. The results obtained are showed in
Table 4.
General procedure for the synthesis of xanthene
derivatives using poly(AMPS-co-AA)
Synthesis of 14-aryl or alkyl-14H-dibenzo [a,j]xanthene
To a mixture of aldehyde (1, 1 mmol) and b-naphthol (2,
2 mmol), crosslinked poly(AMPS-co-AA) (0.04 g) was
added and the mixture was heated on an oil bath at 110 °C
for the reasonable time (Table 2). Completion of the
reaction was indicated by TLC (hexane:ethyl acetate, 8:2).
After completion, appropriate amounts of hot EtOH (96 %)
were added and the mixture stirred for 10 min; then, the
catalyst was separated by filtration. The filtrate was con-
centrated in vacuo to remove the ethanol. The residue was
washed with cold water and crystallized from hot ethanol
to afford the pure products. The desired pure product was
characterized by making a comparison between its physical
data and that known benzoxanthene.
Spectra data for selected compounds
Compound 3b: 1H NMR (100 MHz, CDCl3) d 6.52
(s, 1H), 7.44–8.40 (m, 19H). IR: (KBr disc) cm-1: 3,010,
2,920, 1,580, 1,510, 1,480, 1,460, 1,420, 1,400, 1,240,
1,132.
Compound 3q: 1H NMR (90 MHz, CDCl3) d 3.64
(s, 3H), 6.48 (s, 1H), 6.94–7.62 (m, 15H), 8.07 (s, 1H). IR:
(KBr disc) cm-1: 3,060, 2,930, 1,590, 1,460, 1,420, 1,400,
1,240, 1,110, 800.
Compound 5h: 1H NMR (90 MHz, CDCl3) d 1.01
(s, 6H), 1.14 (s, 6H), 2.24 (m, 4H), 2.50 (m, 4H), 6.14
(s, 1H), 7.12–7.84 (m, 4 H). IR (KBr disc) cm-1: 3,020,
2,982, 1,686, 1,662, 1,460, 1,402, 1,378, 1,240, 1,174.
Compound 5m: 1H NMR (90 MHz, CDCl3) d 1.04 (s,
6H), 1.26 (s, 6H), 2.01 (m, 4H), 2.25 (s, 3H), 2.46 (m, 4H),
5.63 (s, 1H), 6.64–7.16 (m, 4 H). IR (KBr disc) cm-1
:
3,040, 2,970, 2,920, 1,660, 1,620, 1,480, 1,460, 1,360,
1,200, 1,140, 1,000, 870.
Compound 5s: 1H NMR (90 MHz, CDCl3) d 2.01 (m,
4H), 2.12 (m, 4H), 2.42 (m, 4H), 4.86 (s, 1H), 7.01–7.92
(m, 3 H), 8.14 (s, 1H). IR (KBr disc) cm-1: 3,005, 2,960,
2,890, 1,660, 1,615, 1,535, 1,460, 1,330, 1,200, 1,180,
1,120, 960, 840.
Compound 5t: 1H NMR (90 MHz, CDCl3) d 2.04 (m,
4H), 2.20 (m, 4H), 2.52 (s, 3H), 2.64 (m, 4H), 5.21 (s, 1H),
6.91–7.98 (m, 4 H). IR (KBr disc) cm-1: 3,010, 2,970,
Fig. 2 TGA and DTGA thermo grams of AA-co-AMPS polymers.
Heating rate 20 °C/min, under N2
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J IRAN CHEM SOC (2012) 9:757–765
2,890, 1,646, 1,615, 1,480, 1,420, 1,360, 1,200, 1,180,
1,130, 960, 780.
6.84–8.01 (m, 11H). IR: (KBr disc) cm-1: 3,010, 2,980,
2,925, 1,660, 1,590, 1,560, 1,380, 1,230, 1,160, 800.
Compound 5u: 1H NMR (90 MHz, CDCl3) d 2.13 (m,
4H), 2.24 (m, 4H), 2.72 (m, 4H), 3.64 (s, 6H), 5.26 (s, 1H),
7.01–8.12 (m, 3 H). IR (KBr disc) cm-1: 3,040, 2,935,
2,878, 1,655, 1,610, 1,520, 1,440, 1,380, 1,260, 1,190,
1,120, 1,040, 960.
Compound 6l: 1H NMR (90 MHz, CDCl3) d 0.99 (s, 3H),
1.12 (s, 3H), 2.25 (s, 2H), 2.31 (s, 2H), 2.56 (s, 3H), 5.76 (s,
1H), 6.92–7.91 (m, 10H). IR: (KBr disc) cm-1: 3,010,
2,940, 2,890, 1,650, 1,618, 1,530, 1,480, 1,360, 1,230,
1,040, 820.
Compound 5v: 1H NMR (90 MHz, CDCl3) d 2.00 (m,
4H), 2.11 (m, 4H), 2.42 (m, 4H), 5.24 (s, 1H), 6.69–7.23 (d,
2H), 7.46–8.01 (d, 2H). IR (KBr disc) cm-1: 3,002, 2,986,
2,924, 2,894, 1,660, 1,612, 1,510, 1,420, 1,360, 1,220,
1,180, 1,120, 980, 860.
Results and discussion
To the best of our knowledge, crosslinked poly(AMPS-co-
AA) has not been explored in organic synthesis. In con-
tinuation of our interest on application of heterogeneous
catalysts for the development of useful synthesis method-
ology [56–60], we wish to report a simple, efficient and
practical method for the synthesis of xanthene derivatives
using crosslinked poly(AMPS-co-AA) as eco-friendly cat-
alyst with high catalytic activity under solvent-free con-
dition at 110 °C (Scheme 1).
In recent years, solvent-free organic reactions have
caused great interests, which have many advantages such
as high efficiency and selectivity, separation and purifica-
tion, mild reaction conditions, and to benefit industry as
well as environment [61–65].
Compound 5w: 1H NMR (90 MHz, CDCl3) d 1.98 (m,
4H), 2.04 (m, 4H), 2.24 (m, 4H), 4.99 (s, 1H), 7.01–8.11
(m, 4H). IR (KBr disc) cm-1: 3,070, 2,992, 2,935, 2,890,
1,650, 1,610, 1,480, 1,420, 1,200, 1,180, 1,120, 960, 870.
Compound 5x: 1H NMR (90 MHz, CDCl3) d 2.02 (m,
4H), 2.32 (m, 4H), 2.61 (m, 4H), 3.78 (s, 3H), 5.24 (s, 1H),
6.82–7.68 (m, 4 H). IR (KBr disc) cm-1: 3,040, 2,990,
2,934, 2,886, 1,660, 1,614, 1,510, 1,480, 1,360, 1,280,
1,246, 1,190, 1,040, 960, 780.
Compound 6b: 1H NMR (90 MHz, CDCl3) d 0.98 (s,
3H), 1.06 (s, 3H), 2.28 (s, 2H), 2.55 (s, 2H), 5.70 (s, 1H),
7.18–7.82 (m, 12 H). IR: (KBr disc) cm-1: 3,060, 2,980,
2,880, 1,660, 1,480, 1,400, 1,360, 1,230, 1,140.
During our investigation, we chose b-naphthol and
4-chlorobenzaldehyde as model reaction and examined the
amount of crosslinked poly(AMPS-co-AA) as catalyst in
the absence of solvent under various temperatures
(Scheme 1; Table 1). Then, in order to determine the
Compound 6k: 1H NMR (90 MHz, CDCl3) d 1.01 (s,
3H), 1.13 (s, 3H), 2.24 (s, 2H), 2.35 (s, 2H), 5.78 (s, 1H),
OH
Scheme 1 One-pot synthesis of
xanthene derivatives using a
novel polymeric catalyst
2
R
R
O
O
Poly (AMPS-Co-AA)/Solvent-Free/110°C
O
2
RCHO
O
OH
Poly (AMPS-Co-AA)
Solvent - Free/110°C
O
R1
R1
+
R1
R1
3
1
4
2
6
O
O
2
R1
R1
4
R1=CH3,H
R
O
O
R1
R1
R1
R1
O
5
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J IRAN CHEM SOC (2012) 9:757–765
761
absence of the mentioned catalyst no products could be
detected even after 2 h.
Table 1 Screening of the reaction conditions for the synthesis of
14-(4-chlorophenyl)-14H-dibenzo[a,j]xanthene (3b)
After optimization of the reaction conditions, we studied
the generality of these conditions to other substrates. Using
this method, different kinds of aldehydes were reacted with
b-naphthol to produce the corresponding 14-aryl or alkyl-
14H-dibenzo[a,j]xanthene under solvent-free conditions
(Table 2). All the reactions proceeded efficiently within
20–30 min at 110 °C to provide the corresponding xan-
thene derivatives in good yields ranging from 75 to 92 %.
Various aromatic, alkyl and hetroaromatic aldehydes con-
taining electron-withdrawing and electron-donating sub-
stituent at ortho, meta or para positions show equal ease
towards the product formation in good to high yields.
The practical synthetic efficiency of this reaction was
highlighted by the reaction of terephtaldehyde with
b-naphthol to give structurally complex xanthene deriva-
tive (3k) (Scheme 2).
Entry
Amount poly
(AMPS-co-AA)
(g)
Temperature
(°C)
Times
(min)
Yielda
(%)
1
2
3
4
5
6
7
8
9
a
0.02
0.02
0.02
0.02
0.01
0.03
0.04
0.05
–
90
100
110
120
110
110
110
110
110
80
60
55
65
72
72
60
80
92
92
40
40
80
30
30
30
b
120
–
b
Isolated yields, no reaction
optimum reaction conditions, 2 mol of b-naphthol and
1 mol of 4-chlorobenzaldehyde together with a specified
amount of crosslinked poly(AMPS-co-AA) were reacted
under the different temperatures. The results in Table 1
showed some interesting points. First of all, increasing
amount of poly(AMPS-co-AA) did not improve obviously
the yields of 3b. So, the optimum amount of poly(AMPS-
co-AA) was found to be 0.04 g relative to reactants. The
second important point which could be elicited evidently
from these results was that the raising of the reaction
temperature from 110 to 120 °C did not increase the yield
and also did not improve the reaction rates. Also, in
We expected that both of the formyl groups on the
aromatic ring of terephtaldehyde would react with
b-naphthol. However, we observed that one of the formyl
groups was condensed with b-naphthol and another group
was intact because of the steric effects between o-hydro-
gens of benzene ring and the xanthene ring [25]. The most
important of this method is that the acid sensitive func-
tionality present in the molecule remains unaffected. This
fact was amply demonstrated by the reaction of pyridine-3
or 2-carboxaldehyde with b-naphthol, which gave pyri-
dine-3 or 2-yl 14H-dibenzo[a,j]xanthene in good yields
(Scheme 3).
Table 2 The one-pot synthsis
Product (3)
R
Time (min)
Yielda (%)
Mp (°C)
of 14-aryl or alkyl-14H-
dibenzo[a,j]xanthene using
poly(AMPS-co-AA)
Found
Reported
a
b
c
d
e
f
C6H5
30
30
30
25
25
25
25
25
25
25
25
30
30
25
20
20
30
88
92
87
90
92
87
86
80
86
90
90
75
80
83
84
81
89
182–183
290–292
213–215
190–192
298–300
213–214
312–313
259–260
204–206
238–240
309–311
236–237
201–203
228–229
157–158
152–154
171–173
183–185 [25]
289–291 [25]
213–215 [25]
192–193 [31]
298–300 [25]
210–211 [25]
310–312 [25]
258–259 [25]
203–205 [25]
238–240 [25]
310–312 [25]
236–237 [25]
200–202 [25]
226–228 [25]
154–156 [25]
152–154 [25]
–
4-ClC6H4
2-ClC6H4
3-BrC6H4
4-BrC6H4
3-NO2C6H4
4-NO2C6H4
2-CH3OC6H4
4-CH3OC6H4
4-FC6H4
4-CHOC6Hb4
Pyridyl-2-yl
Pyridyl-3-yl
4-CH3C6H4
Isipropyl
g
h
i
j
k
l
a
The yields refer to the
m
n
o
p
q
isolated pure products which
were characterized from their
spectral data and were
compared with authentic
b
sample, b-naphthol/aldehyde
(4:1)
n-Propyl
3-CH3OC6H4
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J IRAN CHEM SOC (2012) 9:757–765
Scheme 2 Reaction between
terephthaldehyde and excess
amount of b-naphthol
CHO
O
CHO
OH
Poly (AMPS-Co-AA)
3k (90%)
+
Solvent-free/110°C
25 min
CHO
4 mmol
1 mmol
O
O
(0%)
Scheme 3 Reaction between
pyridine-3 or 2-carboxaldehyde
with b-naphthol
N
N
R
OH
Poly (AMPS-Co-AA)
or
+
Solvent-free/110°C
25 min
N
O
O
R= 2-CHO or 3-CHO
3l
3m
Encouraged by these results, we replaced the cyclic 1,3-
dicarbonyl compounds (1,3-cyclohexanedione or 5,5-
dimethyl-1,3-cyclohexanedione) instead of b-naphthol in
same conditions (Scheme 1). Initially, we optimized the
amount of poly(AMPS-co-AA) for condensation of the
reaction between 5,5-dimethyl-1,3-cyclohexanedione and
4-chlorobenzaldehyde. The best result was obtained with
0.04 g of poly(AMPS-co-AA). To investigate the versa-
tility of the catalyst, the reaction of cyclic 1,3-dicarbonyl
compounds was carried out with various aldehydes for the
synthesis of 1,8-dioxo-octahydroxanthene under solvent-
free conditions at 110 °C (Table 3). All reactions pro-
ceeded efficiently within 15–25 min at 110 °C to provide
the corresponding xanthene derivatives in good yields
ranging from 68 to 86 %.
poly(AMPS-co-AA) (0.08 g) (Scheme 4). As expected, the
reaction proceeded smoothly for 25 min with yield 80 %
under solvent-free conditions at 110 °C [mp [ 300 °C
(dec.), Lit. [ 300 °C] [47].
Multicomponent reactions (MCRs) have attracted con-
siderable interest because of their expectational synthetic
and practical efficiency [66]. MCRs involve three or more
starting materials reacting in a single flask to form a new
product [67–70]. One example of an MCRs is a three-
component, one-pot synthesis of 12-aryl-8,9,10,12-tetra-
hydrobenzo[a]xanthene-11-ones.
Finally, we have developed this synthetic method for
one-pot efficient synthesis of 12-aryl-8,9,10,12-tetra-
hydrobenzo[a]xanthene-11-ones by polycondensation
aldehydes with b-naphthol and cyclic 1,3-dicarbonyl (1,3-
cyclohexanedione or 5,5-dimethyl-1,3-cyclohexanedione).
For achieving the optimal reaction condition, the reaction
of 4-chlorobenzaldehyde with b-naphthol and 5,5-dime-
thyl-1,3-cyclohexadione in the presence of crosslinked
poly(AMPS-co-AA) was selected as a model reaction and
Following the success from synthesis 1,8-dioxo-octa-
hydroxanthene, we have developed this synthetic method
for the preparation of additional extended bis-1,8-dioxo-
octahydroxanthene derivative in a 4:1 molar ratio of
5,5-dimethyl-1,3-cyclohexanedione to terephtaldehyde to
123

J IRAN CHEM SOC (2012) 9:757–765
763
Table 3 Preparation of
1,8-dioxo-dodecahydroxanthene
using poly(AMPS-co-AA)
Product (5)
R
R1
Time (min)
Yielda (%)
Mp (°C)
Found
Reported
a
b
c
d
e
f
C6H5
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
H
25
25
25
25
25
25
25
25
25
25
25
25
25
15
15
15
15
15
15
15
15
15
15
15
85
85
85
80
82
80
84
86
85
70
68
74
84
72
70
80
82
74
76
82
80
84
80
70
204–205
233–235
225–227
251–252
224–226
170–172
215–217
242–244
225–227
206–208
250–252
166–167
210–212
203–205
229–232
218–220
229–231
249–251
277–279
227–228
180–181
271–273
249–251
216–218
203–204 [47]
230–232 [47]
225–227 [47]
252–254 [47]
222–223 [47]
170–172 [47]
215–217 [47]
240–241 [47]
226–227 [36]
202–205 [39]
247–248 [36]
164–165 [38]
–
4-ClC6H4
2-ClC6H4
2-NO2C6H4
4-NO2C6H4
3-NO2C6H4
4-CH3C6H4
4-BrC6H4
4-FC6H4
g
h
i
j
2-HOC6H4
4-HOC6H4
2-Thiophene
2-CH3C6H4
C6H5
K
l
m
n
o
p
q
r
201–203 [37]
231–223 [37]
216–218 [37]
228–231 [37]
245–247 [37]
–
4-ClC6H4
4-CH3C6H4
4-BrC6H4
4-HOC6H4
3-NO2C6H4
2-CH3C6H4
3,4-CH3OC6H3
4-FC6H4
H
H
H
H
s
H
t
H
–
u
v
w
x
H
–
H
–
2-ClC6H4
2-CH3OC6H3
H
–
H
–
a
Isolated yields
O
dicarbonyl compounds under the catalytic influence of
poly(AMPS-co-AA) (0.06 g) and solvent-free conven-
tional heating, and 12-aryl-8,9,10,12-tetrahydrobenzo[a]
xanthene-11-ones were obtained in high yields. Also, the
tolerance of the present method towards various func-
tionalities present in the substrates viz. halides, methoxy,
hydroxyl and nitro groups generalizes the scope of the
present method.
CHO
O
O
O
O
O
O
Poly (AMPS-co-AA)
+
Solvent-free/110°C
25 min, 80%
CHO
O
In the next step, we investigated the reusability and
recycling of poly(AMPS-co-AA). At first we put 4-chlo-
robenzaldehyde (1 mmol), b-naphthol (2 mmol) and
0.04 g of poly(AMPS-co-AA) together, and then the mix-
ture was stirred at 110 °C for 30 min without any solvent.
When the reaction was completed, the poly(AMPS-co-AA)
was separated by simple filtration by diluting with hot
ethanol, then, dried in oven at 110 °C for 24 h recovered
poly(AMPS-co-AA) was reused in subsequent reactions
(Table 5).
Scheme 4 Reaction between terephthaldehyde with 5,5-dimethyl-
1,3-cyclohexanedione
the effects of the reaction parameters such as amount of
the catalyst and temperature were studied in detail. The
best result was obtained with 0.06 g of poly(AMPS-co-
AA) under solvent-free conditions at 110 °C. Several
structurally diverse aldehydes (Table 4) were subjected
to condensation with b-naphthol and cyclic 1,3-
123

764
J IRAN CHEM SOC (2012) 9:757–765
˚
Mp (C)
Table 4 Preparation 12-aryl-
8,9,10,12-
Product (6)
R
R1
Time (min)
Yielda (%)
tetrahydrobenzo[a]xanthene-11-
ones using poly(AMPS-co-AA)
Found
Reported
a
b
c
d
e
f
C6H5
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
H
40
40
45
50
40
40
35
30
35
30
40
45
50
25
25
25
25
50
75
85
80
78
88
80
80
80
85
88
85
86
74
85
79
85
75
80
150–152
179–181
178–180
220–223
174–175
167–169
182–184
176
151–153 [42, 43]
180–182 [42, 43]
179–180 [42, 43]
223–225 [42, 43]
178–180 [42, 43]
168–170 [42, 43]
185–186 [42, 43]
176–178 [42, 43]
204–205 [42, 43]
163–165 [42, 43]
–
4-ClC6H4
2-ClC6H4
2-NO2C6H4
4-NO2C6H4
3-NO2C6H4
4-FC6H4
g
h
i
4-CH3C6H4
4-CH3OC6H4
2-CH3OC6H4
3-BrC6H4
2-CH3C6H4
2-Thiophene
4-ClC6H4
208–209
167–168
173–175
165–166
182–183
207–208
179–181
233–235
237–239
192–193
J
k
l
–
m
n
o
p
q
r
180–181 [44]
206–208 [46]
180–182 [46]
235–236 [46]
234–235 [46]
189–190 [46]
4-CH3OC6H4
3-NO2C6H4
4-NO2C6H4
C6H5
H
H
H
H
a
Isolated yields
6. M. Ahmad, T.A. King, B.H. Cha, J. Lee, J. Phys. D Appl. Phys.
35, 1473 (2002)
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Table 5 Reuse of the poly(AMPS-co-AA) for synthesis of 3b
Entry
Times (min)
Yielda (%)
0
1
2
a
30
30
40
92
70
65
8. B.B. Bhowmik, P. Ganguly, Mol. Biomol. Spect. 61, 1997 (2005)
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Isolated yields
11. S. Hatakeyama, N. Ochi, H. Numata, S. Takamo, Chem. Com-
mun. (1988) 1202
Conclusions
12. S.V. Ley, I.R. Baxendale, R.N. Bream, P.S. Jackson, A.G. Leach,
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An efficient, heterogeneous, simple and safe procedure for
the preparation of the xanthene derivatives in good yields
and short times was reported in this work. The notable
advantages of this methodology are operational simplicity,
generality, short reaction times and easy work-up.
Acknowledgments The authors are thankful to research council of
Hakim Sabzevari University for financial support.
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