One-pot green and efficient synthesis of xanthenedione derivatives using [C4 (mim) 2](FeCl4)2 as a magnetic room temperature dicationic ionic liquid

Article abstract of DOI:10.13005/ojc/310158

An easily prepared Fe (III)-derived Lewis acid ionic liquid, [C₄ (mim) ₂](FeCl₄)₂,being comprised of dicationic ionic liquid cation and tetrachloroferrate anion, was found to be an efficient, recyclable catalyst

Full text of DOI:10.13005/ojc/310158

ISSN: 0970-020 X
CODEN: OJCHEG
015, Vol. 31, No. (1):
Pg. 483-487
ORIENTAL JOURNAL OF CHEMISTRY
An International Open Free Access, Peer Reviewed Research Journal
2
www.orientjchem.org
One-pot Green and Efficient Synthesis of Xanthenedione
Derivatives using [C (mim) ](FeCl ) as a Magnetic Room
4
2
4 2
Temperature Dicationic Ionic Liquid
1
2
3
BIJAN MOMBAINI GODAJDAR *, ALI REZAKIASAT andALI EZABADI
1
Department of Chemistry, Islamic Azad University Omidiyeh Branch, Omidiyeh, Iran.
Department of Chemistry, College of Science, Shahid Chamran University, Ahwaz, Iran.
Department of chemistry, Faculty of Science,Islamic Azad University, Central Tehran Branch,
2
3
*Corresponding author E-mail: bmombini@gmail.com
http://dx.doi.org/10.13005/ojc/310158
(Received: November 25, 2014; Accepted: January 10, 2015)
ABSTRACT
An easily prepared Fe (III)-derived Lewis acid ionic liquid, [C (mim) ] (FeCl ) , being
4
2
4 2
comprised of dicationic ionic liquid cation and tetrachloroferrate anion, was found to be an efficient,
recyclable catalyst for the synthesis of 1, 8-dioxooctahydroxanthenes by one-pot condensation
reactions of dimedone/ 1, 3- cyclohexanedione with aromatic aldehydes under mild reaction
conditions without utilization of additional organic solvent
Key words: Magnetic room temperature dicationic ionic liquid, 1,
8
-dioxooctahydroxanthen, dimedone, Multi-component reactions, one-pot reaction.
INTRODUCTION
Xanthene derivatives are very important
Magnetic ILs not only have the excellent
properties of IL but also exhibit an unexpectedly
strong response to an additional magnet. These
properties make magnetic ILs have more
advantages and potential application prospects
than conventional ILs in the fields of catalytic
reactions, solvent effects and separation
processes. . Although several types of magnetic
ionic liquids have been created in recent years,
there have been only a few reports about their
applications as catalyst in chemical transformations.
heterocyclic compounds and have been widely
used as dyes fluorescent materials for visualization
of bio-molecules and laser technologies due to their
1
useful spectroscopic properties. They have also
11
been reported for their agricultural bactericide
activity, photodynamic therapy, anti-inflammatory
2
-5
effect,and antiviral activity. Due to their wide range
of applications, these compounds have received a
great deal of attention in connection with their
6
-10
synthesis
.

4
84
MOMBAINI-GOODAJDAR et al., Orient. J. Chem., Vol. 31(1), 483-487 (2015)
In continuation of our work on the catalytic for an appropriate time (Table 2). After completion
1
2-13
properties of magnetic ionic liquids,
herein, we of the reaction (TLC), the mixture was cooled to
wish to report a simple, convenient and efficient room temperature and washed with cooled water.
method for the use of magnetic room temperature The solid product was purified by crystallization from
dicationicionic liquid (MRTDIL)as catalyst for aqueous EtOH to afford products 3a-3m (Scheme
preparation of 1, 8- dioxo- octahydroxanthenes 2).
derivatives.
All the products were fully characterized
EXPERIMENTAL
by spectroscopic data and their melting points are
compared with reported values.
Material and Methods
Melting points were measured on an Spectral data
Electrothermal 9100 apparatus and are 9-(phenyl)-
3,3,6,6-tetramethyl
-
1
13
uncorrected. H & CNMR spectra were recorded 3,4,5,6,7,9- hexahydro-1H-xanthene-1,8-(2H)-
1
on a Bruker Advanced DPX 400 MHz instrument dione (3a): H NMR (CDCl3, 400 MHz) : 1.02 (s,
spectrometer using TMS as the internal standard 6H), 1.13 (s, 6H), 2.19 (d, (2H, J = 16.2 Hz), 2.26 (d,
in CDCl . IR spectra were recorded on a BOMEM 2H, J =16.2 Hz), 2.50 (s, 4H), 4.78 (s, 1H), 7.12 (t,
3
MB-Series 1988 FT-IR spectrometer. Raman 1H, J = 7.2 Hz), 7.24 (t, 2H, J = 7.5 Hz), 7.32 (d, 2H,
1
3
spectroscopy were recorded on a Bruker RFS J= 7.6Hz). C NMR(CDCl , 100 MHz) ä: 27.75,
3
1
00/s Raman spectrometer. Aldehydes, and 29.69, 32.26, 32.61, 41.29, 51.18, 116.07, 126.76,
dimedone were purchased from Merck Company 128.45, 128.80, 144.54, 162.70,
in high purity. Products were characterized by
comparison of their physical and spectroscopic
data with those of known samples.
RESULTSAND DISCUSSION
The acidic MRDIL catalyst was prepared
13
Procedure for the preparation of [C (mim) ]Cl (A) according previously reported (Scheme 1).
4
2
2
1
, 4-Dicholorobutane (1 mmol)was
reacted with 1-methylimidazole (2 mmol),
respectively, stirred in MeOH, refluxed for 24 h, and [C (mim) ](FeCl ) , nuclear magnetic resonance
Due to the paramagnetic nature of the
4
2
4 2
then precipitated from ethyl acetate to obtain the technique could not be used to confirm its structure.
required product (white solid 1a, yield 94%). Instead, UV spectra was used to characterize the
C (mim) ](FeCl ) structure. The UV spectrum is
[
4
2
4 2
Procedure for preparation of [Pbmim](FeCl ) as shown in Figure 1. [C (mim) ](FeCl ) spectra
4
2
4
2
4 2
a magnetic room temperature dicationic ionic exhibited absorption bands in the visible region at
liquid
534, 620 and 680 nm which are characteristic for
C (mim) ](FeCl ) , MRTDIL, was prepared the FeCl4 anion.In order to be able to carry out
-
[
4
2
4 2
by mixing crystal powder of [pbmim]Cl (1 mmol) with preparation of 1, 8- dioxo- octahydroxanthenes
2
anhydrous FeCl (2 mmol) at room temperature for derivatives in a more efficient way minimizing the
3
3h, a dark brown liquid was obtained. The obtained time, temperature and amount of catalyst, the
MRTDIL was extracted with small amount of ethyl reaction of benzaldehyde, and dimedone was
acetate. The solvent was evaporated and the selected as model system to the effects of the catalyst
resulting clear brown liquid was dried in vacuum at different reaction temperatures (25, 60, 80and
oven at 60 °C for 24 h.The MRTDIL was obtained in 100 °Cand the different amount of catalyst (0, 10,
high yield (89%).
20, 30, and 40% mol) were investigated. The
reaction using 20% mol of MRTDIL at 80 °C
General procedure for preparation of 1, 8-dioxo- proceeded in highest yield. Further increase in
octahydro-xanthenes (3a-l)
mixture of
temperature to, 100 °Chad little effect on the rate of
3- reaction. Therefore, we kept the reaction
A
dimedone/1,
cyclohexanedione (2 mmol), aromatic aldehyde (1 temperature at 80 °C as optimal temperature.
mmol) and MRTDIL (20% mol) was heated at 80 °C

MOMBAINI-GOODAJDAR et al., Orient. J. Chem., Vol. 31(1), 483-487 (2015)
485
This reaction was carried out without
catalyst under solvent free conditions in order to
establish the effectiveness of the catalyst. It was
found that 1, 8- dioxo- octahydroxanthenes was
not made after 1h of heating.The best results were
obtained with 1: 2 ratio of benzaldehyde, dimedone,
and 20% mol of MRTDIL after 10 min at 80 °C.
under the above optimal conditions. Unlike some
previously reported methods; the present method does
not require toxic organic solvents to produce the 1,
8-dioxo-octahydroxanthene derivatives
The success of the above reactions
prompted us to investigate the recyclability of
catalyst. We carried out our study by using the
reaction benzaldehyde with dimedone and under
optimal conditions as a model study. For this aim,
after completion of reaction (monitored by TLC),
water was added to the reaction mixture and then
the solid was isolated by filtration. The aqueous
filtrate was then subjected to distillation at 80°C
under reduced pressure (10 mmHg) for 4 h to
recover the IL almost completely. The IL, thus
recovered could bereused five times without loss
of activity for the typical reaction (Fig 2).
After optimizing the conditions, the
generality of this process was demonstrated by the
wide range of substituted aryl aldehydes to synthesize
the corresponding products in excellent yields
(Scheme 2, Table 1). As seen from Table 1, aromatic
aldehydes having electron-donating as well as
electron-withdrawing groups were uniformly
transformed into the corresponding products in high
yields within 10-15 min. Substituent on the aromatic
ring had no obvious effect on yield or reaction time
Table 1: Synthesis of xanthenes derivatives
Entry Ar
Product
R
Time
min)
Yield
M.P (°C)
a
ref
(
(%)
Found
Reported
1
1
1
1
1
4
1
2
3
4
5
6
7
8
9
1
1
1
C H
4-Cl-C H
4-Br-C H
2-Cl-C H
3-Cl-C H
4-NO -C H
2-NO -C H
3-NO -C H
4-OCH -C H
4-CH -C H
4
4-CN-C H
4-CN-C H
3a
3b
3c
3d
3e
3f
3g
3h
3i
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
H
10
10
10
10
10
10
15
15
15
15
15
15
92
90
90
91
91
89
87
89
88
89
90
89
203-204
230-232
240-241
225-227
184-186
222-223
248-249
171-173
241-243
215-217
218-220
268-270
204-205
230-231
240-242
224-226
183-184
6
5
4
6
4
4
4
4
5
4
4
6
6
6
1
4
222
2
6
4
4
4
1
1
1
1
4
4
4
4
246-248
170-172
242-244
217-218
2
6
2
6
3
6
4
0
1
2
3j
3k
3l
3
6
1
6
230
273-275
6
4
4
1
7
6
a
Isolated yield
Table 2:Comparison of results using MDIL
catalyst with results obtained by other workers
Catalyst
Conditions
Time (h)
Yield % Rf
Silica sulfuric acid
InCl .4H O
Solvent- free/80°C
Ionic liquid/80°C
EtOH(reflux)
1-2.5
4-10
6
6
88-97
76-95
84-96
90-98
90-96
87-91
[9]
[6]
[10]
[7]
[8]
-
3
+
2
3
Fe -montmorillonite
NaHSO -SiO
CH CN(reflux)
4
2
3
Amberlyst-15
CH CN(reflux)
5
3
[
C (mim) ](FeCl )
Solvent-free/80°C
0.08- 0.25
4
2
4 2

4
86
MOMBAINI-GOODAJDAR et al., Orient. J. Chem., Vol. 31(1), 483-487 (2015)
The efficiency of MRTDIL (time, yield, 8-dioxooctahydroxanthenes, the results are
reaction conditions) was compared with the presented in Table 2. It is clear that the presented
efficiencies of other catalysts used in synthesis of 1, method is simpler, more efficient and less time
consuming compared with other
Step 1
(
CH )
Cl
2 4 Cl
(CH2)4
N
N
N
N
Cl-
N
Cl-
N
2
MeOH
reflux, 24h
[
C (mim) ]Cl
4 2 2
RDIL (A)
Stepe 2
2FeCl3
(CH )
2 4
N
N
N
N
2
FeCl4
neat condition
RT, 3h
[
C (mim) ](FeCl )
4 2 4 2
(MRTDIL) (B)
Scheme 1: Synthesis of [C (mim) ] (FeCl ) as a magnetic room temperature dicationic ionic liuquid
4
2
4 2
O
Ar
O
O
O
[
C (mim) ](FeCl )
4 2 4 2
2
+
ArCHO
R
R
Solvent-free
O
80°C
R
R
1
0-15 min
R
R
R=H, CH3
1
3a-l
2a-l
Scheme 2: Synthesis of 1, 8-dioxo-octahydro-xanthenes
Fig. 1: Visible spectrum of [C (mim) ](FeCl )
4 2
Fig. 2: Recyclability of the catalyst
4
2

MOMBAINI-GOODAJDAR et al., Orient. J. Chem., Vol. 31(1), 483-487 (2015)
487
CONCLUSION
and reusability and therefore suitable for industrial
applications.
In conclusion, we have successfully
developed a simple and green catalytic procedure
for the efficient synthesis of xanthenes using
MRTDIL and under mild reaction conditions.
MRTDIL can replace the ILs and other
homogeneous catalysts with reasonable recovery
ACKNOWLEDGMENTS
We gratefully thank Islamic Azad
University, Science and Research Branch
Omidiyeh for financial support.
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