Sulfonated Polyethylene Glycol (PEG-SO3H) as Eco-Friendly and Potent Water Soluble Solid Acid for Facile and Green Synthesis of 1,8-Dioxo-Octahydroxanthene and 1,8-Dioxo-Decahydroacridine Derivatives

Article abstract of DOI:10.1080/15533174.2014.900799

In this work, a green, simple, and highly efficient procedure for the preparation of 1,8-dioxo-octahydroxanthene and 1,8-dioxo-decahydroacridine derivatives (as biologically active heterocycles, fluorescence materials and Pharmaceutical compounds) is desc

Full text of DOI:10.1080/15533174.2014.900799

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Sulfonated polyethylene glycol (PEG-SO3H) as eco-
friendly and potent water soluble solid acid for facile
and green synthesis of 1,8-dioxo-octahydroxanthene
and 1,8-dioxo-decahydroacridine derivatives
Alireza Hasaninejada, Mohsen Shekouhya, Marzieh Miara & Somayeh Firoozia
a Department of Chemistry, Faculty of Sciences, Persian Gulf University, Bushehr 75169, Iran
Accepted author version posted online: 18 Feb 2015.
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To cite this article: Alireza Hasaninejad, Mohsen Shekouhy, Marzieh Miar & Somayeh Firoozi (2015): Sulfonated polyethylene
glycol (PEG-SO3H) as eco-friendly and potent water soluble solid acid for facile and green synthesis of 1,8-dioxo-
octahydroxanthene and 1,8-dioxo-decahydroacridine derivatives, Synthesis and Reactivity in Inorganic, Metal-Organic, and
Nano-Metal Chemistry, DOI: 10.1080/15533174.2014.900799
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ACCEPTED MANUSCRIPT
Sulfonated polyethylene glycol (PEG-SO3H) as eco-friendly and potent water soluble solid
acid for facile and green synthesis of 1,8-dioxo-octahydroxanthene and 1,8-dioxo-
decahydroacridine derivatives
Alireza Hasaninejad, Mohsen Shekouhy, Marzieh Miar, Somayeh Firoozi∗
Department of Chemistry, Faculty of Sciences, Persian Gulf University, Bushehr 75169, Iran
Abstract: In this work, a green, simple and highly efficient procedure for the preparation of 1,8-
dioxo-octahydroxanthene and 1,8-dioxo-decahydroacridine derivatives [as biologically active
heterocycles, fluorescence materials and Pharmaceutical compounds] is described. Sulfonated
Polyethylene glycol (PEG-SO3H) has been used as an efficient and reusable catalyst for the one-
pot multi component domino condensation reaction of dimedone and an aromatic aldehyde
o
without/and a primary amine. The reactions were completed at 80 C in water as green solvent.
Using this procedure, all the products were obtained in good to excellent yields. The catalyst has
been recovered and reused several times without any lose of reactivity.
Keywords: green chemistry; sulfonated polyethylene glycol; 1,8-dioxo-octahydroxanthene; 1,8-
dioxo-decahydroacridines; heterocyclic compounds.
* Corresponding author: Address: Department of Chemistry, Faculty of Sciences, Persian Gulf University, Bushehr 75169, Iran. E-mail
addresses: firoozi.org.chem@gmail.com (S. Firoozi).
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Introduction
Functionalized nitrogen and oxygen containing heterocycles play a predominant role in
medicinal chemistry and they have been intensively used as scaffolds for drug development
(1,2). Between them, xanthenes and acridinediones are two important classes of biologically
active heterocycles (3,4).
Xanthene based compounds exhibit extensive activities in pharmaceutical and biological
aspects, for example antibacterial, antiviral and anti-inflammatory activities (5) In particular 1,8-
dioxo-octahydroxanthene derivatives constitute a structural unit in several natural products (6)
and through presence of inbuilt reactive pyran ring they are very important synthons in organic
synthesis. Xanthene derivatives are also very important organic compounds with widespread
applications as dye (7), in laser technologies (8), and fluorescence materials in bio-molecules
visualization (9).
Therefore, a great number of synthetic methods have been reported via the condensation of
aldehyde with 1,3- cyclohexanedione or 5,5-dimethyl-1,3-cyclohexanedione in the presence of
protonic acids (10) or Lewis acids such as InCl3-4H2O (11), FeCl3-8H2O (12), NaHSO4 (13), and
heterogeneous catalysts, for instance Dowex-50W (14), NaHSO4-SiO2 (15), silica sulphuric acid
2-
(16), polyanilinep- toluenesulfonate (17), PPA-SiO2 (18), TiO2/SO4 (19), and Amberlyst-15
(20) as catalysts. Other catalysts, such as trimethylsilyl chloride (21), p-dodecylbenzenesulfonic
acid (22,23), triethylbenzylammonium chloride (24), and NH2SO3/SDS (25) have also been
employed for the preparation of xanthenedione derivatives. Additionally, the above condensation
process could proceed in ionic liquid or ethylene glycol (26) However, some of these
methodologies have some disadvantages, such as low yields (17,18), prolonged reaction time
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(11,15,20,21), harsh reaction conditions (10), and the requirement of excess of catalysts (21) or
special apparatus (23). Thus, the extension of a simple, highly efficient procedure for synthesis
of xanthenes remains desired.
The acridinediones are a class of compounds that exhibit wide applicability as photosensitizers
and as excellent initiators in photopolymerization (27). They have a high fluorescence quantum
yield of about 0.9 (28) and have fine lasing action (29) which operates in the blue green region
with efficiencies comparable to that of coumarin-102 (30). The acridinedione dyes have a
bichromophoric structure enabling them to act as both an electron donor and acceptor (31) The
photochemical behavior of donor-acceptor of these compounds has received considerable
attention due to their unique photophysical, photochemical and nonlinear optical properties (32).
Also, light-emitting materials based on acridinediones have previously reported that they act as
organic light-emitting diodes (OLED) (4). The acridinediones are similar in structure to the 1,4-
dihydropyridines (1,4-DHPs) and the biologically important β-dihydronicotinamide adenine
dinucleotide (NADH) and its analogues which are vital coenzymes in biological systems (33).
The acridinedione dyes have been shown to mimic NADH to a greater extent than the 1,4-DHPs
due to the tricyclic structure which is capable of protecting the enamine moiety (33). The
presence of several reaction centers in acridinediones opens broad synthetic possibilities (34).
Furthermore, the chemical behaviors of acridinediones in catalytic hydrogenation reactions under
various conditions have been studied (35).
Numerous acridinediones have been prepared by the reactions between β-diketones with
various aldehydes and appropriate amines, in most cases primary amine, to form a fluorescent
heterocyclic system via various methods (36,37). In addition, these synthetic methods have been
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catalyzed by utilizing various catalysts such as p-dodecylbenzenesulfonic acid (DBSA) under
microwave irradiation (38), Brønsted acidic imidazolium salts containing perfluoroalkyl tails
(39), and 1-Methylimidazolium triflouroacetate ([Hmim]TFA) (10).
In recent years, there has been rapid growth in the development of novel polymer-supported
compounds (40), such as supported catalysts, reagents, and scavengers. These species allow
rapid and simplified procedures, and their use has become widespread in solution-phase organic
synthesis and combinatorial chemistry (41). In this context, soluble polymers have recently been
the subject of an intense research activity; allowing the reaction to be carried out in
homogeneous solution they would secure higher chemical and stereochemical efficiency than
insoluble polymer (42). Among the soluble polymeric matrixes employed, poly(ethylene glycol)s
(PEGs) are the most successful. Provided that their Mw is >2000 Da, PEGs are soluble in many,
mostly polar solvents (including water) and insoluble in a few nonpolar solvents (hexanes,
diethyl ether, tert-butyl methyl ether). Because of this solubility profile, PEG-based supports
combine the advantageous features of homogeneous solution chemistry (high reactivity, lack of
diffusion phenomena, analytical simplicity) and of solid phase methods (ready isolation and
purification of products) (26,40).
Use of aqueous media as a reaction solvent has attracted much attention in synthetic organic
chemistry for several reasons (43). In comparison with organic solvents, water is cheap, safe and
reduces the use of harmful organic solvents and leads to the development of environmentally
friendly chemical processes (44). In addition, reactions in aqueous media illustrate unique
reactivities and selectivities that are not usually observed in organic media (45). However,
organic solvents are still used instead of water for mainly two reasons; first, most organic
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substrates are not soluble in water, and as a result, water cannot function as a reaction medium.
Second, many reactive substrates, reagents, and catalysts are sensitive towards water and are
decomposed or deactivated in aqueous media. A possible new way to improve the solubility of
substrates is the use of surface-active compounds that can form micelles (46) or vesicular
structures. Polyethylene glycols are soluble in water by continues repeated (-OCH2CHO-) units
that have lipophilic properties and can work as surfactant reagent that is able to provide micelles
of water insoluble reactant to encourage the organic reactions in aqueous media (Figure 1).
In continues of our recent studies about use of green protocols in organic synthesis (47-55),
herein we report the use of sulfonated polyethylene glycol as a potent and eco-friendly catalyst
for facile and green synthesis of 1,8-dioxo-octahydroxanthene derivatives under solvent-free
condition and also synthesis 1,8-dioxo-decahydroacridines derivatives at the present sulfonated
polyethylene glycol as potent water soluble solid acid catalyst in water (Scheme 1).
Results and Discussion
To achieve the best results we examined the efficiency of different reaction media and catalyst
amounts for the condensation reactions of 5,5-dimethy-1,3-cyclohexanedione (1) and
benzaldehyde (2) as a model reaction (Scheme 2) and obtained result was reported in table 1. For
each reaction condition, conversion of 5,5-dimethy-1,3-cyclohexanedione (2 mmol) and
benzaldehyde (1 mmol) to 3,3,6,6-Tetramethyl-9-phenyl-3,4,5,6,7,9-hexahydro-2H-xanthene-
1,8-dione (3a) was monitored by thin layer chromatography (TLC) using hexane-ethyl acetate
(5:1) as eluent. As it can be seeing from table 1, significant rate enhancement and improved
yields were observed using about (20 mol% in order of active H+) of PEG-SO3H under solvent-
free condition at 80 oC.
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The experimental procedure for this reaction is remarkably simple and does not require the use
of organic solvents or inert atmospheres. Use of PEG-SO3H as catalyst provided very simple
work up procedure. After completion of the reaction, water was added and the insoluble products
was separated by simple filtration and purified by recrystalization from ethanol.
The generality of the method has been shown by the preparation of a series of 1,8-dioxo-
octahydroxanthene derivatives using various aromatic aldehydes bearing electron withdrawing
and electron releasing substituents and 1,3-5,5-dimethyl-1,3-cyclohexanedione (Table 2). The
influence of electron-withdrawing and electron-donating substituents on the aromatic ring of
aldehydes upon the reaction yields was investigated. The results showed that both electron-
withdrawing and electron- releasing substituents had no significant effect on the reaction yields.
Moreover, the presence of halogen on the aromatic ring of aldehydes had negligible effect on the
reaction results. We also successfully applied acid sensitive heteroaromatic aldehydes and the
corresponding products were obtained without any by-products or side reactions.
Our methodology for synthesis of 1,8-dioxo-octahydroxanthene derivatives also shown very
good chemoselectivity. The use of PEG-SO3H as a water soluble solid acid catalyst showed rate
enhancements, high yields and good reaction times. However, one of the important points
regarding the adaptable catalyst is its ability to recovering from reaction media and stability of
their reactivity toward the eternal uses. From every reaction the PEG-SO3H catalytic system have
been recovered by evaporation of water after filtration of insoluble products. Table 3 shows the
results of five consecutive runs of the reaction of 5,5-dimethyl-1,3-cyclohexanedione with
benzaldehyde and shows that catalyst could be reused several times without noticeable loss of
activity. This reusability demonstrates the high stability and turnover of PEG-SO3H catalytic
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system under operating condition.
In the other way, the catalytic effects of PEG-SO3H for the synthesis of 1,8-dioxo-
decahydroacridines were studied. For this propose, dimedone (2 mmol), benzaldehyde (1 mmol)
and aniline (1 mmol) were selected as a model reaction to achieve 3,3,6,6-tetramethyl-9,10-
diphenyl-3,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione 5a in different conditions and the
results are summarized in Table 4 (Scheme 3).
After extensive screening, we found that the optimized best yields and time profiles were
o
obtained with 10 mol % of PEG-SO3H in water as solvent at 90 C. It is noticeable that neither
water nor aqueous solutions of H2SO4 have been shown efficiency for this reaction under same
conditions.
Using the optimum conditions including the utilization of primary aromatic amine (1 mmol),
dimedone (2 mmol), an aromatic aldehydes (1 mmol) and catalytic amount of PEG-SO3H (10
mol %) in water as solvent at 90 °C were tested (Table 5). As can be seen from table 5 (5a-q),
steric and electronic variation in the aromatic aldehyde were tolerated and did not change the
efficiency of the reaction in the presence of aromatic amine. Besides the introduction of key
functional group such as halides, alkyl, nitro, methoxy and nitrile, several aromatic aldehydes
bearing two functional groups were also tested and resulted in the corresponding products.
From every reaction the PEG-SO3H catalytic system have been recovered by evaporation of
water after filtration of insoluble products. Table 6 shows the results of five consecutive runs of
the reaction of 5,5-dimethyl-1,3-cyclohexanedione, benzaldehyde with aniline and shows that
catalyst could be reused several times without noticeable loss of activity. This reusability
demonstrates the high stability and turnover of PEG-SO3H catalytic system under operating
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condition.
Experimental section
All chemicals were purchased from Merck or Fluka Chemical Companies. All compounds are
1
13
known, and their structures were identified by comparing their melting points and H and C
1
13
NMR data with those reported in the literature. The H NMR (500 MHz) and C NMR (125
MHz) were run on a Bruker Avance DPX-250, FT-NMR spectrometer (δ in ppm). Melting
points were recorded on a Büchi B-545 apparatus in open capillary tubes.
Preparation of PEG-SO3H
At 0 oC, chlorosulfonic acid (1.16 g, 10 mmol) was added to a solution of PEG-4000 (6.0 g, 1
mmol) in CH2Cl2 (10 mL). Then the resulting solution was stirred at room temperature
overnight, and the solution was concentrated under vacuum. Appropriate ether (50 ml) was
added, and the precipitate filtered and washed with ether (30 ml) three times to afford the PEG-
SO3H (61).
General procedure for the preparation of 1,8-dioxo-octahydroxanthene derivatives
,5-dimethyl-1,3-cyclohexanedione (2 mmol) and aromatic aldehyde (1 mmol) were mixed with
o
PEG-SO3H (1.2 g, 0.2 mmol) and the obtained mixture was stirred magnetically at 80 C. After
the completion of reaction (as monitored by TLC) warm water (5 ml) was added and the mixture
stirred for about 5 min. The insoluble crude product was filtered and recrystallized from EtOH
and the pure product was obtained. In order to recover the catalyst, the filtrate was dried under
reduced pressure and recovered catalyst was washed with diethyl ether and reused after drying
under reduced pressure.
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General procedure for the preparation of 1,8-dioxo-decahydroacridine derivatives
o
PEG-OSO3H (0.6 g, 0.1 mmol) was dissolved in water (5 ml) and heated to 90 C and then
5,5-dimethyl-1,3-cyclohexanedione (2 mmol), aromatic aldehyde (1 mmol) and primary amine
were added and obtained mixture was stirred. After the completion of reaction (as monitored by
TLC), insoluble products was separated by simple filtration and then was recrystalized from
EtOH to obtain pure products. In order to recover the catalyst, the filtrate was dried under
reduced pressure and recovered catalyst was washed with diethyl ether and reused after drying
under reduced pressure.
Selected spectral data of the products
9-(4-fluorophenyl)-3,4,6,7-tetrahydro-3,3,6,6-tetramethyl-10-p-tolylacridine-
o
1,8(2H,5H,9H,10H)-dione (5l). White powder (M.P.= 258-261 C) υmax (KBr): 3400, 2950,
1
1620, 1480, 1440, 1370, 1270, 1080, 1010, 880, 540 cm-1. H-NMR (CDCl3, 500 MHz) δ: 0.83
(s, 6H), 0.98 (s, 6H), 1.87 (d, J=17.5 Hz, 2H), 2.11, (d, J=17.5 Hz, 2H), 2.16 (d, J=16.0 Hz, 2H),
2.23 (d, J=16.0 Hz, 2H), 2.52 (s, 3H), 5.28 (s, 1H), 6.96 (t, J=8.7 Hz, 2H), 7.12 (d, J=8.0 Hz,
2H), 7.38 (d, J=7.5 Hz, 2H), 7.41-7.44 (m, 2H) ppm. Calculated for C30H32FNO2: C, 78.75; H,
7.05; N, 3.06%. Found: C, 78.53; H, 7.26; N, 2.91%.
Conclusion
In conclusion, we have developed a simple, green and efficient procedure for synthesis of 1,8-
dioxo-octahydroxanthene and 1,8-dioxo-decahydroacridine derivatives catalyzed by PEG-SO3H.
The use of mild conditions, simple work-up, high yield, and recyclability of the catalyst make
our methodology a valid contribution to the existing processes in the field of 1,8-dioxo-
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octahydroxanthene and 1,8-dioxo-decahydroacridine derivatives synthesis. Furthermore, the
method was successfully applied for aldehydes bearing powerful electron releasing substituents
and their corresponding 1,8-dioxo-octahydroxanthene and 1,8-dioxo-decahydroacridine
derivatives were obtained in good yields.
Acknowledgments
The authors thank the Research Committee of Persian Gulf University for financial support of
this work.
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(56) Venkatesan, K.; Pujari, S.S.; Lahoti, R.J.; Srinivasan, K.V. Ultrason. Sonochem. 2008,
15, 548-553.
(57) Zhang, Z.H.; Liu, Y.H. Cat. Comm. 2008, 9, 1715-1719.
(58) Niknam, Kh.; Panahi, F.; Saberi, D.; Mohagheghnejad, M. J. Heterocyclic Chem. 2010,
47, 292-300.
(59) Paliwal, P.; Jetti, S.R.; Bhatewara, A.; Kadre, T.; Jain, S. ISRN. Org. Chem. 2013, 2013,
1-6.
(60) Bose, D.S.; Kumar, R.K. Tetrahedron Lett. 2006, 47, 813-816.
14

ACCEPTED MANUSCRIPT
(61) Wang, X.; Quan, Z.; Wang, F.; Wang, M.; Zhang, Z.; Li, Z. Synth. Commun. 2006, 36,
451-456.
15

ACCEPTED MANUSCRIPT
Table 1. Comparison of the reaction of dimedone (2 mmol) with benzaldehyde (1 mmol) under
various conditions and in the presence of different amounts of PEG-SO3H.
Catalyst amount
Temperature
(°C)
Time
(min)
450
450
90
Yielda
(%)
50
Entry
Solvent
(mol%)
20
1
2
3
4
5
6
7
CHCl3
THF
reflux
20
reflux
Trace
85
MeOH
EtOH
CH2Cl2
EtOAc
H2O
20
reflux
20
reflux
270
280
300
480
75
20
reflux
60
20
reflux
70
20
reflux
25
Solvent-
free
8
9
20
20
100
90
70
65
90
91
Solvent-
free
10
11
12
13
14
15
Solvent-
free
Solvent-
free
Solvent-
free
Solvent-
free
Solvent-
free
Solvent-
free
20
20
20
20
5
80
70
50
r.t.
80
80
60
92
89
240
420
600
330
180
87
Trace
70
10
75
16

ACCEPTED MANUSCRIPT
16
17
Solvent-
free
15
25
80
80
120
65
82
92
Solvent-
free
a Isolated Yield
17

ACCEPTED MANUSCRIPT
Table 2. Preparation of 1,8-dioxo-octahydroxanthene derivatives via condensation of dimedone
(2 mmol) and aromatic aldehydes (1 mmol) under solvent-free condition in the presence of PEG-
SO3H (20 mol %) at 80 oC.
Entry
1
Ar
C6H5
Product Time (min) Yielda (%) M.P. Found (Reported) (ref)
60
165
30
92
81
91
89
96
98
89
94
86
96
90
90
83
84
89
97
95
89
202-204 (201-203) (21)
238-240 (240-242) (21)
228-230 (230-232) (21)
184-186 (185-187) (18)
223-225 (224-226) (11)
226-227 (224-226) (11)
213-215 (210-212) (11)
170-172 (170-171) (56)
221-223 (222-224) (11)
167-169 (168-170) (22)
242-244 (241-243) (11)
215-217 (217-218) (57)
252-254 (250-252) (57)
188-190 (190-192) (56)
176-179 (175-176) (57)
207-209 (210-212) (57)
174-176 (174-176) (58)
61-63 (62-64) (56)
3a
3b
3c
3d
3e
3f
2
4-Br-C6H4
3
4-Cl-C6H4
4
3-Cl-C6H4
210
120
90
5
2-Cl-C6H4
6
4-F-C6H4
7
4-Me-C6H4
4-isopropyl-C6H4
4-NO2-C6H4
3-NO2-C6H4
4-OMe-C6H4
4-CN-C6H4
2-NO2-C6H4
3-Br-C6H4
45
3g
3h
3i
8
160
95
9
10
11
12
13
14
15
16
17
18
60
3j
210
190
375
215
135
75
3k
3l
3m
3n
3o
3p
3q
3r
3,4-(OMe)2-C6H3
3,4,5-(OMe)3-C6H2
-CH=CH-C6H5
2-furyl
160
75
18

ACCEPTED MANUSCRIPT
19
20
2-pyrolyl
2-thienyl
110
80
83
89
88-90 (88-90) (59)
3s
3t
163-165 (164-165) (57)
a Isolated Yield
19

ACCEPTED MANUSCRIPT
Table 3. Reusability of the catalyst for a series of five consecutive runs of the reaction of
dimedone (2 mmol) with benzaldehyde (1 mmol).
Entry Time (min) Conversion (%) Yielda (%)
1
2
3
4
5
90
100
100
100
100
100
92
92
92
92
92
90
90
100
120
a Isolated Yield
20

ACCEPTED MANUSCRIPT
Table 4. Comparison of the reaction of dimedone (2 mmol) with benzaldehyde (1 mmol) and
anilin (1 mmol) under various conditions.
Temperature
(°C)
reflux
reflux
reflux
reflux
reflux
reflux
reflux
r.t.
Time
(min)
480
480
480
360
480
480
235
480
480
480
240
480
240
230
480
Yielda
(%)
20
Entry
Solvent
Catalyst (mol%)
1
2
CHCl3
THF
PEG-SO3H (10)
PEG-SO3H (10)
PEG-SO3H (10)
PEG-SO3H (10)
PEG-SO3H (10)
PEG-SO3H (10)
PEG-SO3H (10)
PEG-SO3H (10)
PEG-SO3H (10)
PEG-SO3H (10)
PEG-SO3H (10)
PEG-SO3H (5)
PEG-SO3H (15)
PEG-SO3H (20)
Catalyst-free
Trace
75
3
MeOH
EtOH
CH3CN
EtOAc
H2O
4
80
5
47
6
10
7
80
8
H2O
Trace
35
9
H2O
50
10
11
12
13
14
15
H2O
70
71
H2O
90
82
H2O
90
73
H2O
90
82
H2O
90
82
H2O
90
Trace
Solvent-
free
16
17
PEG-SO3H (10)
aqueous H2SO4
90
90
480
180
----b
38
H2O
21

ACCEPTED MANUSCRIPT
(10)
a Isolated Yield
b
Mixture of 3,3,6,6-tetramethyl-9-phenyl-3,4,5,6,7,9-hexahydro-1H-xanthene-
3a and 3,3,6,6-tetramethyl-9,10-diphenyl-3,4,6,7,9,10-
1,8(2H)-dione
hexahydroacridine-1,8(2H,5H)-dione 5a
22

ACCEPTED MANUSCRIPT
Table 5. Preparation of 1,8-dioxo-decahydroacridine derivatives via condensation of dimedone
(2 mmol), aromatic aldehydes (1 mmol) and primary amine (1 mmol) in the presence of PEG-
SO3H in water and 90 oC.
Entry
1
Ar
Ar'
C6H5
Product Time (min) Yielda (%) M.P. Found (Reported) (ref)
C6H5
240
300
240
240
82
81
85
89
83
87
87
83
81
85
79
83
84
82
81
73
82
255-256 (255-256) (20)
219-222 (220-222) (20)
278-281 (276-278) (60)
266-268 (265-267) (60)
273-276 (270-271) (60)
318-320 (315-317) (60)
289-291 (285-287) (60)
352-354 (350-352) (60)
282-285 (285-287) (60)
296-298 (293-294) (60)
268-270 (267–269) (58)
258-261
5a
5b
5c
5d
5e
5f
2
4-OMe-C6H4
3-NO2-C6H4
C6H4
C6H5
3
C6H5
4
4-Me-C6H4
4-Me-C6H4
4-Me-C6H4
5
4-Cl-C6H4
3-Cl-C6H4
210
6
240
7
3-NO2-C6H4 4-Me-C6H4
4-OH-C6H4 4-Me-C6H4
4-OMe-C6H4 4-Me-C6H4
4-Me-C6H4 4-Me-C6H4
4-Cl-C6H4 3-OH-C6H4
5g
5h
5i
180
8
360
270
240
300
240
180
240
300
240
240
9
10
11
12
13
14
15
16
17
5j
5k
5l
4-F-C6H4
4-Me-C6H4
4-NO2-C6H4 2-OH-C6H4
3-NO2-C6H4 3-CN-C6H4
3-OH-C6H4 3-CN-C6H4
4-SMe-C6H4 4-Me-C6H4
3-CN-C6H4 4-Me-C6H4
a Isolated Yield
296-298 (>300) (58)
267-269 (266–268) (58)
309-311 (>300) (58)
240-242 (239) (58)
5m
5n
5o
5p
5q
254-257 (256–257) (58)
23

ACCEPTED MANUSCRIPT
Table 6. Reusability of the catalyst for a series of five consecutive runs of the reaction of
dimedone (2 mmol) with benzaldehyde (1 mmol) and aniline (1 mmol).
Entry Time (min) Conversion (%) Yielda (%)
1
2
3
4
5
240
100
100
100
100
100
82
80
81
82
80
240
260
300
350
a Isolated Yield
24

ACCEPTED MANUSCRIPT
Figure 1. Performance of PEG-SO3H as a surfactant reagent in water.
25

ACCEPTED MANUSCRIPT
Scheme
1. Preparation of 1,8-dioxo-octahydroxanthene and 1,8-dioxo-decahydroacridines
derivatives.
26

ACCEPTED MANUSCRIPT
Scheme . Synthesis of 3,3,6,6-tetramethyl-9-phenyl-3,4,5,6,7,9-hexahydro-1H-xanthene-
2
1,8(2H)-dione 3a using dimedone and benzaldehyde in different conditions.
27

ACCEPTED MANUSCRIPT
Scheme 3. Synthesis of 3,3,6,6-tetramethyl-9,10-diphenyl-3,4,6,7,9,10-hexahydroacridine-
1,8(2H,5H)-dione 5a using aniline, dimedone and benzaldehyde in different conditions.
28