Solvent-free synthesis of quinoline derivatives via the Friedl?nder reaction using 1,3-disulfonic acid imidazolium hydrogen sulfate as an efficient and recyclable ionic liquid catalyst

Article abstract of DOI:10.1016/j.crci.2013.10.007

A convenient, highly versatile and eco-friendly protocol for the synthesis of quinoline derivatives via the Friedl?nder reaction is presented. The method is based on the use of 1,3-disulfonic acid imidazolium hydrogen sulfate (DSIMHS) as an efficient and

Full text of DOI:10.1016/j.crci.2013.10.007

C. R. Chimie 17 (2014) 370–376
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Full paper/Memoire
Solvent-free synthesis of quinoline derivatives via the
Friedla¨nder reaction using 1,3-disulfonic acid imidazolium
hydrogen sulfate as an efficient and recyclable ionic
liquid catalyst
*
*
Farhad Shirini , Asieh Yahyazadeh , Kamal Mohammadi,
Nader Ghaffari Khaligh
Department of Chemistry, College of Science, University of Guilan, Rasht, 41335, I.R. Iran
A R T I C L E I N F O
A B S T R A C T
Article history:
A convenient, highly versatile and eco-friendly protocol for the synthesis of quinoline
derivatives via the Friedla¨nder reaction is presented. The method is based on the use of
1,3-disulfonic acid imidazolium hydrogen sulfate (DSIMHS) as an efficient and reusable
ionic liquid catalyst. A variety of ketones afforded the substituted quinolines in excellent
yields during relatively short reaction times under solvent-free conditions; the catalyst
could be easily recovered and reused for several times without any appreciable loss of
activity.
Received 5 April 2013
Accepted after revision 10 October 2013
Available online 21 February 2014
Keywords:
Quinolines
Ionic liquid
ß 2013 Acade´mie des sciences. Published by Elsevier Masson SAS. All rights reserved.
Friedla¨nder annulation
Solvent-free conditions
1. Introduction
Owing to such significance, the synthesis of quinoline
and its derivatives has been an attractive goal for
Quinoline and its derivatives are important intermediates
in organic synthesis and exhibit various physiological
properties and pharmacological activities, such as antipar-
asitic [1], antitubercular [2], antifilarial [3], anti-platelet [4],
HMG-CoA reductase inhibiting [5], anti-allergic, anti-inflam-
matory [6–9], anti-asthmatic [10,11], antibacterial [12–15],
antihypertensive [16,17], anticancer [18–21], tyrosine kinase
inhibitory agents [22], anti-proliferative [23], antimalarials
[24,25], and antifungals [26,27]. Furthermore, these com-
pounds find applications in chemistry of transition metal
catalysts for uniform polymerization and luminescence
chemistry [28]. Quinoline derivatives also act as antifoaming
agents in refineries [29]. They are used in a variety of nano-
structures and meso-structures with enhanced electronic and
photonic functions [30–32].
the organic and medicinal chemists. Several methods for
the synthesis of the quinoline nucleus have been reported
in the literature, including Skraup, Doebner–von Miller,
Friedla¨nder, Pfitzinger, Conrad–Limpach, and Combes
[33].
These classical methods are well known and still
frequently used for the preparation of pharmaceutically
important materials bearing a quinoline backbone. Among
them, the Friedla¨nder synthesis is one of the simplest and
most frequently used pathways to quinoline derivatives
that involve a condensation reaction between an aromatic
o-aminoaryl ketone or aldehyde with another carbonyl
compound containing an activated
a-methylene group
followed by cyclodehydration [34,35]. The reaction can be
catalyzed by strong acids or bases or may take place
without a catalyst at higher temperatures. However, both
harsh reaction conditions and the need for a strong acid
or base catalyst, which is incompatible with either acid-
or base-sensitive groups, reduce the synthetic scope of
this reaction. Also, under basic or thermal conditions
*
Corresponding authors.
E-mail addresses: shirini@guilan.ac.ir, fshirini@gmail.com (F. Shirini),
yahyazadeh@guilan.ac.ir (A. Yahyazadeh).
1631-0748/$ – see front matter ß 2013 Acade´mie des sciences. Published by Elsevier Masson SAS. All rights reserved.
http://dx.doi.org/10.1016/j.crci.2013.10.007

F. Shirini et al. / C. R. Chimie 17 (2014) 370–376
371
sometimes ortho-aminobenzophenone does not react
with simple ketones or -keto esters [36]. In general,
better yields of quinolines were achieved under acid
catalysis [37].
Several Brønsted acid catalysts such as hydrochloric
acid in water [38], sulfamic acid [39], sulfuric acid [40],
dodecylphosphonic acid [41], p-toluenesulfonic acid, and
polyphosphoric acid [42], PEG-supported sulfonic acid
[43], propylsulfonic silica [44], o-benzenedisulfonimide
[45], oxalic acid [46] and H3PW12O40 [47] have been widely
used for this purpose.
groups, obviously enhances their acidities and water
solubility [99,100]. Moreover, their polar nature makes
them useful for use under solvent-free conditions. Recently,
sulfonic acid-functionalized ionic liquids received great
attention due to their interesting properties like environ-
mental compatibility, reusability, greater selectivity, and
ease of isolation. They are used as dual solvent-catalyst
[101], for several organic reactions, such as esterification
[102], alkylation [103], nitration of aromatic compounds
[104], hydrolysis [105] and heterocyclic synthesis, like
Fisher indole synthesis [106]. Imidazolium ILs having a
Brønsted acidic group such as DSIMHS [107,108] are
important and they have been successfully used as catalyst
in organic synthesis. According to the above-mentioned
considerations and our interest in ILs chemistry, we have
decided to develop an efficient and mild method for the
synthesis of quinoline and its derivatives using the
Friedla¨nder annulation method in the presence of DSIMHS
as an efficient catalyst, under solvent-free conditions.
b
Also, modified methods, employing Lewis acids such as
Zr(NO3)4 or Zr(HSO4)4 [48], LASC [49], ceric ammonium
nitrate [50], GdCl3.6H2O [51], BiCl3 [52], Ag3PW12O40 [53],
SnCl2 [54], FeCl3 [55], Mg(ClO4)2 [56], Nd(NO3)3 [57],
Y(OTf)3 [58], NiCl2 [59], Bi(OTf)3 [60], ZnCl2 [61], NaAuCl4
[62], NaF [63], NiCl2Á2H2O [46] and other effective agents
and methods, such as I2/CAN [64], SiO2/I2 [65], NaHSO4–
SiO2 [66], PMAÁSiO2 [67], Amberlyst 15 [68], microwave
[69], urea [70], KOtBu [71], sodium ethoxide (10 mol %)
[72], nanosized MCM-41 [73], nanocrystalline aluminium
oxide [74] and Nano-Flake ZnO [75] have been reported for
this reaction. However, most of these methods suffer from
many disadvantages such as harsh reaction conditions, use
of harmful organic solvents, high reaction temperatures,
prolonged reaction times, low yields, difficulties in the
work-up, use of relatively expensive reagents, low selectiv-
ity and tedious experimental procedure. In several cases the
recovery of the catalyst is also a problem. Therefore,
development of simple, convenient, and environmentally
benign methods for this synthesis is still required.
In recent years, ionic liquids (ILs) have gained much
attention as ‘‘designer solvents’’ for a variety of chemical
applications. These compounds are composed of ions and
are liquid at or close to room temperature. ILs have become
increasingly popular as reaction and extraction media in
research and development. These compounds have also
widely been used as powerful alternatives to the volatile
organic compounds in the field of organic synthesis. In
addition, the synthesis of task-specific ionic liquids
(TSILs), which have a functional group in their framework,
may expand the application of ILs in organic chemistry
[76–78].
2. Experimental
2.1. General
Chemicals were purchased from Fluka and Merck
Chemical Companies and used without further purification.
All yields refer to isolated products and Progress of the
reactions was monitored by TLC using silica gel polygrams
SIL G/UV 254 plates. The products were characterized by
comparison of their spectral (IR, 1H NMR and 13C NMR) and
physical data with those of authentic samples.
2.2. Instrumentation
Melting points were recorded on an electrothermal
digital melting point apparatus model IA9100 in open
capillary tubes. IR spectra were recorded using a Perkin-
Elmer model Spectrum One FT-IR Spectrometer. The 1H
NMR spectra were obtained on a Bruker DRX-400 Avance
spectrometer and 13C NMRs were recorded on a Bruker
DRX-100 Avance spectrometer (d in ppm).
There have been many researches referring to some
aspects of TSILs in physical chemistry, electrochemistry,
designability of structure and catalytic ability [79–95].
They have received attention as eco-friendly and alter-
native reaction media in organic synthesis because of their
unique properties, such as high chemical and thermal
stability, cost effectiveness, air and water compatibility,
negligible vapor pressure, non-miscibility, non-flamm-
ability, good reactivity and excellent electrical conductiv-
ity and ease of handling [96,97]. For this reason, recently,
the field of TSILs is growing at a very fast rate, as the many
beneficial properties of these liquids are identified and
utilized. Among them, Brønsted acidic ILs had been
identified as more effective and environmentally friendly
catalysts and could catalyze those organic unit reactions
which were promoted by the stronger acids [98].
2.3. General procedure for the synthesis of quinoline
derivatives in the presence of DSIMHS
A mixtureof 2-aminoarylketone (1 mmol), a-methylene
carbonyl compound (1.5 mmol) and DSIMHS (0.25 mmol)
was heated in an oil bath at 70 8C under stirring for the
appropriate time mentioned in Table 3. After completion of
the reaction as monitored by TLC, the reaction mixture was
washed with water, because DSIMHS is soluble in water and
the product was precipitated with high purity. Then the
crude solid product was filtered off and recrystallized from
ethanol.
2.4. The spectral and analytical data for new compound are
given below
Introduction of Brønsted acidic functional groups into
cations or anions of ILs, especially SO3H and SO4H functional
8-chloro-10-phenyl-11H-indeno[1,2-b] quinolin-11-
one (Table 3, entry 15).

372
F. Shirini et al. / C. R. Chimie 17 (2014) 370–376
MP 240–243 8C; IR (KBr) n
max/cmÀ1: 3046, 2917, 2850,
Table 1
Temperature optimization for the synthesis of ethyl 2-methyl-4-
phenylquinoline-3-carboxylatea.
1717, 1612, 1572, 1504, 1443; 1H NMR (400 MHz, CDCl3):
d (ppm) 7.43–7.46 (m, 2H), 7.51–7.55 (td, J1 7.60 Hz, J2
0.80 Hz, 1H), 7.60–7.634 (m, 3H), 7.66–7.67 (d, J 2.00 Hz,
1H), 7.69–7.70 (d, J 2.40 Hz, 1H), 7.72–7.75 (m, 1H), 8.10–
8.15 (t, J 9.80 Hz, 2H); 13C NMR (100 MHz, CDCl3): d (ppm)
121.7, 123.3, 124.0, 127.4, 128.4, 128.7, 129.3, 129.4, 131.3,
131.8, 132.4, 133.1, 135.5, 137.5, 143.1, 147.1, 148.8, 162.2,
189.9.
Entry
Temperature (8C)
Time (min)
Yield (%)
1
2
3
4
25
60
70
80
300
30
5
30
56
94
96
5
a
Reaction condition: 2-aminobenzophenon (1 mmol), EAA (1.5 mmol)
and DSIMHS (0.25 mmol) at different temperatures under solvent-free
conditions.
3. Results and discussion
The reaction of 2-aminobenzophenon and ethyl acet-
oacetate (EAA) was chosen as a model for finding the
optimization conditions and to achieve good yield of the
desired products. In order to investigate the effect of
temperature on the reaction, the concentration of ionic
liquid was kept constant at 0.25 mmol and a mixture of
substrates was treated with DSIMHS. The reaction was
monitored by TLC at different temperatures ranging from
25 to 80 8C under solvent-free conditions (Table 1).
Our results indicate that after stirring the reaction
mixture at room temperature for 300 min under solvent-
free conditions, the yield of the corresponding product was
low (Table 1, entry 1). Subsequently, the mixture was
heated in an oil bath. Increasing the reaction temperature
from 60 to 70 8C gave better results in terms of yield and
reaction time. Further increase in temperature did not
show any significant improvement in the yield and the
reaction time. Therefore, 70 8C was selected as the reaction
temperature for all further reactions.
Then, we changed the catalyst amount and examine
the effect of this variation on the reaction. According to the
results presented in Table 2, in the absence of DSIMHS, the
reaction did not produce any product, even after 3 h, which
showed that the catalyst exhibits a high catalytic activity in
this transformation (Table 2, entry 1). So, the best result
was obtained using 0.25 mmol of DSIMHS for this reaction.
Higher amounts of the catalyst improved neither the yield
nor the reaction time further.
On the basis of the above-mentioned studies, we
concluded that the best results can be obtained when the
relative ratio of the substrate/EAA/DSIMHS was 1.0 mmol/
1.5 mmol/0.25 mmol, respectively, while the reaction is
carried out at 70 8C undersolvent-free conditions. Under the
optimized conditions, the model reaction gave a 94% yield of
ethyl 2-methyl-4-phenylquinoline-3-carboxylate after
5 min (Table 2, entry 3 and Scheme 1).
Thereafter, to show the generality of this method, a
series of ortho-aminoaryl ketones were reacted with
various 1, 3-dicarbonyl compounds under the optimized
conditions and the results are summarized in Table 3.
Table 2
Temperature optimization for the synthesis of ethyl 2-methyl-4-
phenylquinoline-3-carboxylatea.
Entry
Catalyst amount (mmol)
Time (min)
Yield (%)
1
2
3
4
–
180
30
5
–
0.15
0.25
0.35
76
94
96
5
a
Reaction condition: 2-aminobenzophenon (1 mmol), EAA (1.5 mmol)
and different amounts of DSIMHS at 70 8C under solvent-free conditions.
As shown in Table 3, this method is equally effective for
cyclic ketones, both cyclic and acyclic diketones and
b-
ketoesters. These types of compounds are reacted smoothly
with 2-aminobenzophenone and 2-amino-5-chlorobenzo-
phenone to produce a range of quinoline derivatives.
Complete conversion and good-to-excellent isolated yields
were observed for all the substrates employed. This reaction
is very effective in avoiding the use of strong mineral acids,
high temperatures, and toxic and polluting reactants.
All synthesized products are known compounds and
were characterized by comparing their melting points, IR,
1H and 13C NMR spectra, with those of authentic samples.
The reusability and recyclability of DSIMHS was also
examined in the reaction of 2-aminobenzophenon and EAA
at 70 8C under solvent-free conditions. For this purpose, the
catalyst was easily recovered from the reaction mixture by
a simple extraction with water. Then the recovered
catalyst was dried and reused at least for four times
without considerable loss of its activity (Fig. 1).
Furthermore, in order to show the excellent catalytic
activity of DSIMHS and the efficiency of this procedure, we
have compared some of the results obtained by our
method with some of those reported in the literature, as
shown in Table 4; the obtained results indicate the
superiority of the present method in terms of yields
and/or reaction times.
There are two possible reaction mechanisms that are
shown in Scheme 2. The carbonyl group is activated by
Ph
Ph
N
O
O
O
DSIMHS, 0.25 mmol
O
OEt
+
OEt
Solvent-free
70 oC
NH2
Scheme 1. Reaction of 2-aminobenzophenone and EAA under solvent-free condition at 70 8C in the presence of DSIMHS.

F. Shirini et al. / C. R. Chimie 17 (2014) 370–376
373
Table 3
Synthesis of quinolines in the presence of DSIMHS under solvent-free conditions at 70 8Ca.
Entry
2-Aminoaryl ketone
Ketone
Quinoline
Time (min)
Yield (%)b
94
M.P. (8C)
Found
Ref.
Lit.
1
5
99–100
100–101
[46]
[109]
[46]
[53]
[53]
[53]
[53]
[41]
[46]
[53]
[46]
[53]
Ph
O
O
O
O
O
Ph
O
OEt
OEt
N
NH2
2
12
15
15
5
93
92
90
94
92
89
92
94
91
88
89
99–100
109–110
129–131
153–154
155–157
192–194
100–101
132–134
150–152
106–108
164–166
98–100
Ph
O
O
O
O
O
O
O
O
O
O
O
O
Ph
O
OMe
O
Me
N
NH2
3
111–112
130–132
156–157
155–156
190–192
102–104
133–135
150–151
106–107
164–165
Ph
O
Ph
O
N
NH2
4
Ph
Ph
O
N
NH2
5
Ph
Ph
O
N
NH2
6
10
25
20
45
35
25
30
O
Ph
O
Ph
O
N
NH2
7
O
Ph
O
Ph
O
N
NH2
8
Ph
O
O
O
O
Ph
Cl
Cl
Cl
OEt
OEt
O
N
NH2
Ph
9
Ph
N
O
Cl
OMe
O
O
Me
O
NH2
Ph
10
11
12
Ph
Cl
Cl
Cl
Cl
O
N
NH2
Ph
Ph
Cl
O
N
NH2
Ph
Ph
Cl
O
N
NH2

374
F. Shirini et al. / C. R. Chimie 17 (2014) 370–376
Table 3 (Continued )
Entry
2-Aminoaryl ketone
Ketone
Quinoline
Time (min)
20
Yield (%)b
89
M.P. (8C)
Found
Ref.
Lit.
13
186–187
185–186
[53]
O
O
O
Ph
Ph
N
O
Cl
Cl
Cl
Cl
O
NH2
14
15
a
40
20
90
88
207–209
240–243
208–209
[53]
Ph
O
O
Ph
O
Cl
Cl
N
Ph
N
NH2
This work
–
O
O
Ph
O
O
NH2
Products were characterized by their physical constants, comparison with authentic samples, IR and NMR spectroscopy.
Isolated yield.
b
DSIMHS
+
O
DSIMHS
Ph
HO
R2
R1
Ph
NH2
+
H
O
(a)
O
R2
Ph
N
R2
R2
R1
R1
R1
NH2 O
Ph
Ph
R2
R1
R2
R1
R2
R1
-H2O
-H2O
O
N
H
NH2
OH
(I)
(b)
DSIMHS
R2
O
Ph
O
+
Ph OH
N
R2
R1
O
R2
R1
Ph
R1
+
NH2
N
H
(II)
-H2O
Ph
R2
R1
+
HSO4
N
N
DSIMHS =
N
HO3S
SO3H
Scheme 2. Proposed reaction mechanism.

F. Shirini et al. / C. R. Chimie 17 (2014) 370–376
375
Acknowledgments
We are thankful to the University of Guilan Research
Council for the partial support of this work. F. Shirini and
K. Mohammadi wish to thank the Sobhandarou Pharma-
ceutical Company for the supply of some of the facilities in
this work.
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In conclusion, we have successfully demonstrated a green
approach for the synthesis of quinoline derivatives via
Friedlander annulation using DSIMHS as an efficient, reusable
and environmentally acceptable catalyst under solvent-free
conditions. The major advantages of this procedure include
fast reaction times, moderate reaction conditions, high con-
versions, ease of preparation and separation of the catalyst,
excellent yields, and avoidance of the usage of environmen-
tally unfavorable organic solvents and toxic catalysts. Also, the
catalyst was successfully recovered and recycled at least for
four runs without significant loss in its activity, which proves
that this method is much more convenient than those with
conventional catalysts.
´
´
´
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