Journal of Molecular Liquids 160 (2011) 4049

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Journal of Molecular Liquids

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m o l l i q

An environmental friendly approach for the synthesis of highly substituted

imidazoles using Brnsted acidic ionic liquid, N-methyl-2-pyrrolidonium hydrogen
sulfate, as reusable catalyst
Hamid Reza Shaterian , Mohammad Ranjbar
Department of Chemistry, Faculty of Sciences, University of Sistan and Baluchestan, PO Box 98135-674, Zahedan, Iran

a r t i c l e

i n f o

Article history:
Received 14 January 2011
Received in revised form 14 February 2011
Accepted 16 February 2011
Available online 24 February 2011

a b s t r a c t
Brnsted acidic ionic liquid, N-methyl-2-pyrrolidonium hydrogen sulfate, has been used as an efcient and
reusable catalyst for the one-pot synthesis of 2,4,5-trisubstituted and 1,2,4,5-tetrasubstituted imidazoles
under thermal solvent-free conditions in excellent yields.
2011 Elsevier B.V. All rights reserved.

Keywords:
N-methyl-2-pyrrolidonium hydrogen sulfate
2,4,5-trisubstituted imidazoles
1,2,4,5-tetrasubstituted imidazoles
Solvent-free
Ionic liquid
Catalyst

1. Introduction
Multi-component reactions (MCRs) are powerful tools in
generating products in organic and medicinal chemistry for their
high degree of atom economy and application in the diversityoriented convergent synthesis of complex organic molecules from
simple and readily available substrates in a single synthetic
operation [1,2].
Imidazoles are an important class of heterocycles being the core
fragment of different natural products and biological systems [3].
Compounds containing imidazole moiety have many pharmacological
properties and play important roles in biochemical processes [4].
Substituted imidazoles that can be used as light-sensitive materials in
photography are known as inhibitors, fungicides and herbicides [5],
plant growth regulators and therapeutic agents [6].
Ionic liquid (IL) technology offers a new and environmentally
benign approach toward modern synthetic chemistry. Ionic liquids
have interesting advantages such as extremely low vapor pressure,
excellent thermal stability, reusability, and talent to dissolve many
organic and inorganic substrates [7]. Ionic liquids have been
successfully employed as solvents and catalyst for a variety of
reactions [811], which promise widespread applications in industry
and organic syntheses.

Corresponding author. Tel.: +98 541 2446565; fax: +98 541 2431067.
E-mail address: hrshaterian@chem.usb.ac.ir (H.R. Shaterian).
0167-7322/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.molliq.2011.02.012

In continuation of our effort to develop Lewis and Brnsted acid

catalyzed synthetic methodologies [1215], we report herein, a
simple synthesis of 2,4,5-trisubstituted (Scheme 1) and 1,2,4,5tetrasubstituted imidazoles (Scheme 2) in high yields using Brnsted
acidic ionic liquid, N-methyl-2-pyrrolidonium hydrogen sulfate, as a
catalyst for the rst time.
2. Experimental
All reagents were purchased from Merck and Aldrich and used
without further purication. All yields refer to isolated products after
purication. Products were characterized by comparison with
authentic samples and by spectroscopy data (IR, 1H NMR and 13C
NMR spectra). The NMR spectra were recorded on a Bruker Avance
DPX 500 MHz instrument. The spectra were measured in DMSO-d6
relative to TMS (0.00 ppm). FT-IR spectra were recorded on a JASCO
FT-IR 460 plus spectrophotometer. Mass spectra were recorded on an
Agilent technologies 5973 network mass selective detector (MSD)
operating at an ionization potential of 70 eV. TLC was performed on
silica-gel Poly Gram SIL G/UV 254 plates.
2.1. Preparation of N-methyl-2-pyrrolidonium hydrogen sulfate as
ionic liquid
N-methyl-2-pyrrolidone (20 mmol) was charged into a 150 mL
three necked ask with a magnetic stirrer. Then equimolar concentrated sulfuric acid (98 wt.%) was added dropwise slowly into the

H.R. Shaterian, M. Ranjbar / Journal of Molecular Liquids 160 (2011) 4049

41

Ph
Ph

Ph

CHO

O
or
O

+ NH4OAC+ NH4OAC

+
X1

Catalyst
Solvent-Free
Thermal

Ph
N

X1

Ph

Ph

OH
Catalyst = Bronsted acidic ionic liquid, N-methyl-2-pyrrolidonium hydrogen sulfate
Scheme 1. Condensation reaction between benzil or benzoin, benzaldehyde, and ammonium acetate at 100 C in the presence of N-methyl-2-pyrrolidonium hydrogen sulfate as
Brnsted acidic ionic liquid.

ask at 80 C for 12 h. The mixture was washed with diethyl ether

three times to remove non-ionic residues and dried in vacuum by a
rotary evaporator to obtain the viscous clear N-methyl-2-pyrrolidonium hydrogen sulfate [16].
2.2. General procedure for preparation of 2,4,5-trisubstituted imidazoles
Benzil or benzoin (1 mmol), aldehyde (1 mmol), and ammonium
acetate (4 mmol) were added to N-methyl 2-pyrrolidone hydrogen
sulfate (0.08 g, 0.4 mmol) in an oil bath at room temperature. The
resulting mixture was heated to 100 C for the appropriate time reported in
Table 1. After completion of the reaction which was monitored by TLC, the
mixture washed with water, the solid product puried by recrystallization
from ethanol. All of the desired product(s) were characterized by
comparison of their physical data with those of known compounds.
Some characterization data for selected known products are given below.
2-(4-methoxyphenyl)-4,5-diphenylimidazole (Table 1, Entry 4): 1H
NMR (DMSO-d6, 500 MHz): =12.48 (s, 1H), 8.00 (dt, J =8.80 Hz, 2.0 Hz,
2H), 7.51 (d, J=7.2 Hz, 4H), 7.35 (t, J=7.2 Hz, 4H), 7.27 (t, J =7.2 Hz, 2H),
7.04 (dt, J=8.8 Hz, 2.0 Hz, 2H), 3.80 (s, 3H); 13C NMR (DMSO-d6,
125 MHz): =55.2, 114.1, 122.9, 126.7, 127.0, 127.7, 128.4, 145.6, 159.4,
ppm; IR (KBr, cm 1): 3400, 3060, 1611, 1490, 1179, 1028, 830, 761.
2-(2,4-Dichlorophenyl)-4,5-diphenylimidazole (Table 1, Entry
18): 1H NMR (DMSO-d6, 500 MHz): = 12.8 (s, 1H), 7.80 (d,
J = 8.4 Hz), 7.81 (s, 1 H), 7.617.22 (m, 12H) ppm; 13C NMR
(DMSO-d6, 125 MHz): = 126.7, 127.2, 127.4, 127.9, 128.2, 128.3,
128.7, 128.8, 129.6, 130.6, 132.4, 132.6, 133.9, 134.8, 137.1,
142.4 ppm; IR (KBr, cm 1): 3427, 3068, 1593, 824, 767.
For recycling the catalyst, after washing solid products with water
completely, the water containing ionic liquid (IL is soluble in water) was
evaporated under reduced pressure and ionic liquid was recovered and
reused.
2.3. General procedure for preparation of 1,2,4,5-tetrasubstituted
imidazoles
Benzil or benzoin (1 mmol), aldehyde (1 mmol), amine (1 mmol),
and ammonium acetate (1 mmol) were added to N-methyl-2pyrrolidonium hydrogen sulfate (0.08 g, 0.4 mmol) in an oil bath at

room temperature. The resulting mixture was heated to 100 C for the
appropriate time reported in Table 2. After completion of the reaction
which was monitored by TLC, the mixture was washed with water,
and the solid product puried by recrystallization from ethanol. All of
the desired product(s) were characterized by comparison of their
physical data with those of known compounds. Some characterization
data for selected known products are given below.
1,4,5-Triphenyl-2-p-tolyl-1H-imidazole (Table 2, Entry 6): 1H
NMR (DMSO-d6, 500 MHz): = 2.26 (s, 3 H), 7.08 (d, J = 8.0 Hz,
2H), 7.167.18 (m, 1H), 7.227.25 (m, 6 H), 7.267.28 (m, 5H), 7.31
7.32 (m, 3H), 7.50 (d, J = 8.0 Hz, 2H) ppm; 13C NMR (DMSO-d6,
125 MHz): = 21.5, 127.2, 128.4, 128.9, 129.0, 129.2, 129.50, 129.58,
129.6, 129.9, 131.3, 131.9, 132.0, 135.3, 137.60, 137,63, 138.6,
147.0 ppm; IR (KBr, cm 1): 2935, 1590, 1577, 1492.
1,2-Bis(4-chlorophenyl)-4,5-diphenyl-1 H-imidazole (Table 2,
Entry 10): 1H NMR (DMSO-d6, 500 MHz): = 7.177.19 (m, 1 H),
7.237.25 (m, 4H), 7.297.32 (m, 5H), 7.387.42 (m, 6H), 7.50 (d,
J = 7.0 Hz, 2H) ppm; 13C NMR (DMSO-d6, 125 MHz): = 127.2, 127.4,
129.44, 129.49, 129.9, 130.1, 130.8, 130.9, 131.3, 132.0, 132.3, 134.1,
134.3, 135.0, 136.2, 145.8 ppm; IR (KBr, cm 1): 2987, 1596, 1499,
1411.
For recycling the catalyst, after washing solid products with water
completely, the water containing ionic liquid (IL is soluble in water)
was evaporated under reduced pressure and ionic liquid was
recovered and reused.
3. Results and discussion
Owing to the versatile biological activities of substituted imidazoles numerous classical methods for the synthesis of these
compounds have been reported [36]. In a typical procedure, benzil
or benzoin, aldehydes, amines, and ammonium acetate are condensed
in the presence of strong protic acid such as H3PO4 [13], H2SO4 [14],
HOAc [15] as well as organo catalyst in HOAc [9] under reux
conditions. These homogeneous catalysts present limitations due to
the use of corrosive reagents and the necessity of neutralization of the
strong acid media. In addition, the synthesis of these heterocycles in
polar organic solvents such as ethanol, methanol, acetic acid, DMF and
DMSO lead to complex isolation and recovery procedures.

Ph
Ph

Ph

NH2

CHO

O
or
O
Ph

+
X1

X2

N
+ NH4OAC

Catalyst
Solvent-Free
Thermal

Ph
N
X2

X1

Ph
OH
Catalyst = Bronsted acidic ionic liquid, N-methyl-2-pyrrolidonium hydrogen sulfate

Scheme 2. Condensation reaction of benzil or benzoin, benzaldehydes, anilines, and ammonium acetate using N-methyl-2-pyrrolidonium hydrogen sulfate as catalyst at 100 C.

42

H.R. Shaterian, M. Ranjbar / Journal of Molecular Liquids 160 (2011) 4049

Table 1
Synthesis of 2,4,5-trisubstituted imidazoles via a one-pot pseudo four-component reaction in the presence of N-methyl-2-pyrrolidonium hydrogen sulfate as Brnsted acidic ionic
liquid (0.08 g, 0.4 mmol) under thermal solvent-free condition at 100 C.
Entry

Aldehydes

Reaction time (h)

Yield %

M.P/C

Benzil

Benzoin

Benzil

Benzoin

Found

Reported[Ref.]

1.5

87

86

270

269[19]

2.5

89

85

233236

232235[20]

2.5

87

90

203206

205207[21]

2.5

2.5

83

78

231233

230232[21]

85

80

210

210210.5[21]

1.5

78

89

217220

216218[22]

1.5

2.5

95

97

233

233[19]

96

92

204207

205[23]

1.5

95

90

270273

272[17]

10

1.5

1.5

93

89

261263

260.5262[24]

11

1.5

1.5

96

98

287289

285287[18,25]

12

2.5

92

97

176178

176.5177[26]

13

2.5

95

93

196198

195197[27]

H.R. Shaterian, M. Ranjbar / Journal of Molecular Liquids 160 (2011) 4049

43

Table 1 (continued)
Entry

Aldehydes

Reaction time (h)

Yield %

M.P/C

Benzil

Benzoin

Benzil

Benzoin

Found

Reported[Ref.]

14

1.5

97

95

263

262264[21]

15

98

92

242243

241242[18]

16

1.5

96

98

N265

N260[18]

17

2.5

2.5

89

87

269271

270[17]

18

1.5

2.5

95

97

176178

176.5177[26]

19

1.5

1.5

92

95

200202

201202[28]

20

2.5

90

92

261263

261.5263.5[21]

21

1.5

2.5

92

90

189191

189190[27]

22

1.5

1.5

92

98

256258

257258[27]

23

1.5

2.5

95

95

202204

202203[28]

24

2.5

87

80

242243

243[17]

25

90

98

290292

291.5292[21]

26

2.5

90

92

242243

241242[29]

(continued on next page)

44

H.R. Shaterian, M. Ranjbar / Journal of Molecular Liquids 160 (2011) 4049

Table 1 (continued)
Entry

Aldehydes

Reaction time (h)

Yield %

M.P/C

Benzil

Benzoin

Benzil

Benzoin

Found

Reported[Ref.]

1.5

2.5

93

95

243244

242244[30]

2.5

2.5

92

97

260262

260261[27]

29

3.5

90

92

200201

200201[27]

30

2.5

93

97

199

197[31]

31

3.5

78

82

261262

261[17]

27

28

CHO

Yields refer to isolated pure products. The known products were characterized and compared for their physical properties (M.p, 1H NMR, 13C NMR and FT-IR) with authentic samples.

Table 2
Synthesis of 1,2,4,5-tetrasubstituted imidazoles via a one-pot four component condensation reaction in the presence of N-methyl-2-pyrrolidonium hydrogen sulfate as Brnsted
acidic ionic liquid (0.08 g, 0.4 mmol) under thermal solvent-free condition at 100 C.
Entry

Aldehydes

Amines

Reaction time/min

Yield %

Benzil

Benzoin

Benzil

Benzoin

Found

M.P/C
Reported[Ref.]

20

25

90

95

220221

218[32]

30

35

95

93

159160

158160[32]

35

40

75

73

211213

208211[33]

40

50

76

78

125127

124126[33]

45

60

70

78

152154

151153[33]

30

35

80

87

200203

189[32]

30

35

82

78

164165

165166[32]

H.R. Shaterian, M. Ranjbar / Journal of Molecular Liquids 160 (2011) 4049

45

Table 2 (continued)
Entry

Aldehydes

Amines

Reaction time/min

Yield %

Benzil

Benzoin

Benzil

Benzoin

Found

M.P/C
Reported[Ref.]

40

55

80

82

201203

201202[32]

20

25

97

90

172175

170172[34]

10

15

20

96

98

188200

187189[33]

11

20

25

97

95

146149

149151[33]

12

15

20

93

98

221223

219220[33]

13

20

25

91

95

160162

156158[33]

14

15

20

97

98

197199

196197[33]

15

20

25

92

95

167168

163165[34]

16

45

45

89

87

190193

188191[33]

17

35

45

85

93

130133

128130[34]

18

20

25

98

95

149152

146148[34]

19

55

60

85

80

164167

164[34]

20

30

35

90

92

155157

156157[34]

(continued on next page)

46

H.R. Shaterian, M. Ranjbar / Journal of Molecular Liquids 160 (2011) 4049

Table 2 (continued)
Entry

Aldehydes

Amines

Reaction time/min

Yield %

Benzil

Benzoin

Benzil

Benzoin

Found

M.P/C
Reported[Ref.]

21

20

25

92

95

135137

134135[34]

22

40

45

87

75

158161

157160[35]

23

20

30

95

95

281284

280281[36]

24

25

35

86

90

229231

226228[37]

25

35

45

92

89

200203

199202[38]

26

25

30

95

90

299291

289290[38]

27

20

25

90

95

200201

198201[38]

28

20

35

87

92

233234

230232[37]

29

45

45

90

95

216218

215217[38]

30

40

45

85

89

219221

218220[38]

31

35

45

87

83

188190

185187[37]

H.R. Shaterian, M. Ranjbar / Journal of Molecular Liquids 160 (2011) 4049

47

Table 2 (continued)
Entry

Aldehydes

Amines

Reaction time/min

Yield %

Benzil

Benzoin

Benzil

Benzoin

Found

M.P/C
Reported[Ref.]

32

45

55

89

83

185

184186[34]

33

20

25

97

95

250253

248251[37]

34

60

65

80

78

106108

104105[34]

35

25

25

89

92

161163

165167[33]

36

20

30

90

96

141142

140142[34]

37

25

35

92

95

154155

150152[34]

38

20

25

95

97

186187

183185[37]

39

25

30

85

90

145146

144146 [37]

40

45

55

85

82

113116

112115[33]

Yields refer to isolated pure products. The known products were characterized and compared for their physical properties (M.p, 1H NMR, 13C NMR and IR) with authentic samples.

First report, the condensation reaction of benzil or benzoin

(1 mmol), aldehyde (1 mmol), and ammonium acetate (4 mmol) in
the presence of ionic liquid, N-methyl-2-pyrrolidonium hydrogen
sulfate (0.08 g, 0.4 mmol), as catalyst produces 2,4,5-trisubstituted
imidazoles under solvent-free conditions at 100 C (Scheme 1).
The stoichiometric amount of ammonium acetate in the preparation of 2,4,5-trisubstituted imidazoles is 2. We can prepare 2,4,5trisubstituted imidazoles using two equivalents of ammonium acetate
but we observed in our experiment and other published papers, if we
use inexpensive and available ammonium acetate having more than
two equivalents, the reaction will show better results. Thus, a slight
excess of the ammonium acetate was found to be advantageous and
hence the molar ratio of benzil or benzoin to ammonium acetate was
kept at 1:4. The efciency and versatility of the ionic liquid as catalyst
for the preparation 2,4,5-trisubstituted imidazoles were demonstrated by the wide range of substituted and structurally diverse aldehydes
to synthesize the corresponding products in high to excellent yields

(Table 1). The presence of electron donating groups on the aromatic

aldehyde resulted in the corresponding products in low yields and the
reaction was sluggish, however the presence of electron-withdrawing
groups afforded the corresponding 2,4,5-trisubstituted imidazoles in
shorter reaction time with higher yields. Also, benzil in comparison
with benzoin gives corresponding products in shorter reaction time
rather than benzoin but there was no effect in the yield of
corresponding 2,4,5-trisubstituted imidazoles.
Next, as part of our program aimed at developing useful new synthesis
methods based on the use of mentioned ionic liquid as a catalyst, we have
studied the four-component one-pot synthesis of 1,2,4,5-tetrasubstituted
imidazoles by condensing benzil or benzoin (1 mmol), aldehyde
(1 mmol), amine (1 mmol), and ammonium acetate (1 mmol) using a
catalytic amount of N-methyl-2-pyrrolidonium hydrogen sulfate (0.08 g,
0.4 mmol) under solvent-free conditions at 100 C.
The substrate scope of the reaction was then evaluated using a
variety of structurally diverse aldehydes and amines. Both aliphatic and

48

H.R. Shaterian, M. Ranjbar / Journal of Molecular Liquids 160 (2011) 4049

Table 3
Comparison of the efciency of various catalysts with N-methyl-2-pyrrolidonium hydrogen sulfate in the synthesis of 2,4,5-trisubstituted imidazoles.
Entry

Catalyst

Conditions

Time (min)

Yield (%)

Ref.

1
2
3
4
5
6
8
9

InCl33H2O
KH2PO4
Yb(OPf)3
Zr(acac)4
L-proline
[H bim]BF4
NiCl26H2O/Al2O3
N-methyl-2-pyrrolidonium hydrogen sulfate

MeOH/R.T
Reux in EtOH
C10F18/80 C
Reux in EtOH
Methanol/60 C
100 C
Reux in EtOH
100 C

492
60
360
120
540
60
90
60

76
89
80
95
87
94
89
98

[39]
[40]
[41]
[42]
[23]
[19]
[43]
Present work

Based on the preparation of 2-(4-nitrophenyl)-4,5-diphenyl-1H-imidazole (Table 1, Entry 15).

Table 4
Comparison of the efciency of various catalysts with N-methyl-2-pyrrolidonium hydrogen sulfate in the synthesis of 1,2,4,5-tetrasubstituted imidazoles.
Entry

Catalyst

Conditions

Time (min)

Yield (%)

Ref.

1
2
3
4
5
6
7
8
9
10

BF3/SiO2
SiO2
NaHSO4/SiO2
InCl33H2O
L-proline
AlCl3
MgCl2
SnCl4
K5CoW12O40.3H2O
N-methyl-2-pyrrolidonium hydrogen sulfate

140 C
CH2Cl2/R.T
140 C
140 C
Methanol/R.T
Methanol/60 C
140 C
140 C
140 C
100 C

120
120
120
440
540
120
120
120
120
30

92
90
92
79
88
53
50
60
95
98

[41]
[44]
[33]
[39]
[23]
[41]
[41]
[32]
[37]
Present work

Based on the preparation of 1-benzyl-4,5-diphenyl-2-P- tolyl-1H-imidazole (Table 2, Entry 7).

corresponding imidazoles (Table 2, Entries 35, 8, 19, 34). The presence

of electron donating groups on the aromatic aldehydes and aromatic
anilines resulted in the corresponding products in low yields and the
reaction was sluggish, however the presence of electron-withdrawing

aromatic aldehydes and primary amines could be subjected successfully to this protocol. Aromatic aldehydes and amines produced high
yields of 1,2,4,5-tetrasubstituted imidazoles, whereas aliphatic aldehydes and amines produced moderate to lower yields of the

N
H

H3C

O
O S O
O
NH4OAC
H

O
H

N
H3C H
Ph

Ph

-H2O

Ph

NH4OAC

Ph

NH3

O
R
O S O
O
H

HN

(II)

NH3

R
H

+H

NH

(III)

(I)
H

Ph

O
O S O
O

N
R

Ph

N
H

Ph OH
NH
CH
Ph
NH R

H CH3
N

-H+

Ph
Ph

N H
R
N
H

-H2O

Ph OH
NH
CH
Ph
R
N
H
(IV)

Scheme 3. Mechanism of condensation reaction between benzil, benzaldehyde, and ammonium acetate in the presence of N-methyl-2-pyrrolidonium hydrogen sulfate as Brnsted
acidic ionic liquid.

H.R. Shaterian, M. Ranjbar / Journal of Molecular Liquids 160 (2011) 4049

49

ammonium acetate in a pseudo four-component reaction and affords

the corresponding 2,4,5-trisubstituted imidazoles in high yields. Also
this recyclable catalyst has been used for preparation of 1,2,4,5tetrasubstituted imidazoles by one-pot four-component condensation
of benzil or benzoin, aldehydes, amines and ammonium acetate in
excellent yields under solvent-free and conventional heating conditions. The recovered ionic liquid was reused for seven cycles without
loss of its activities.

Acknowledgments
We are thankful to the University of Sistan and Baluchestan
Research Council for the partial support of this research.

References
Fig. 1. The recycling of the N-methyl-2-pyrrolidonium hydrogen sulfate as Brnsted
acidic ionic liquid under solvent-free conditions.

groups afforded the corresponding 1,2,4,5-tetrasubstituted imidazoles

in shorter reaction times with higher yield. Also, benzil reacts in shorter
reaction time rather than benzoin but without any effect on the yields.
To show the merit of the present work in comparison with
reported results in the literature, we compared results of N-methyl-2pyrrolidonium hydrogen sulfate with reported catalysts in the
synthesis of 2,4,5-trisubstituted and 1,2,4,5-tetrasubstituted imidazoles. As shown in Tables 3 and 4, the ionic liquid can act as a suitable
catalyst with respect to reaction times and yields of the products.
The proposed mechanism for the reaction using ionic liquid as
catalyst is also described for the preparation of 2,4,5-trisubstituted
imidazoles from the reaction of benzil, aldehyde and ammonium
acetate in Scheme 3. According to literature report [17,18], hydrogen
bonding can occur between the solute (benzil) and the cationic
(N+\H) or ionic component (SO
4 \H) of ionic liquid. Brnsted acidic
ionic liquid, N-methyl-2-pyrrolidonium hydrogen sulfate can activate
the carbonyl groups of benzil and aldehydes to decrease the energy of
transition state. Then nucleophilic attack of the nitrogen of ammonia
obtained from NH4OAc on the activated carbonyl group, resulted in
the formation of aryl aldimine (I) and -imino ketone (II), and it
followed by the nucleophilic attack of the in-situ generated imine to
carbonyl of aryl aldimine giving the intermediate (III). Their
subsequent intramolecular interaction leads to cyclization and
eventually to the formation of intermediate (IV) which dehydrates
to the 2,4,5-trisubstituted imidazoles.
We also investigated the recycling of the catalyst under solventfree conditions using a model reaction of 4-methylbenzaldehyde
(1 mmol), benzylamine (1 mmol), benzil (1 mmol), and ammonium
acetate (1 mmol) (Table 2, Entry 7). After completion of the reaction,
water was added and the precipitated mixture was ltered off for
separation of crude products. After washing the solid products with
water completely, the water containing ionic liquid (IL is soluble in
water) was evaporated under reduced pressure and ionic liquid was
recovered and reused (Fig. 1). We also calculate turnover frequency
(TOF) to discuss the activity of the catalyst. The substrate conversion
percentage to the product was 100% and TOF obtained 5 h 1. The
recovered catalyst was reused seven runs without any loss of its
activities and the activity (TOF) did not decrease.
4. Conclusions
N-methyl-2-pyrrolidonium hydrogen sulfate efciently catalyzes
the condensation reaction of benzil or benzoin, aldehydes and

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