ScienceAsia 39 (2013): 50–55

R ESEARCH ARTICLE
doi: 10.2306/scienceasia1513-1874.2013.39.050

Benzoin condensation of aromatic aldehydes catalysed by

N,N -dimethylbenzimidazolium iodide and NaOH under
green conditions
Viwat Hahnvajanawong∗ , Wijitra Waengdongbung, Surachai Piekkaew, Baramee Phungpis,
Parinya Theramongkol
Department of Chemistry and Centre of Excellence for Innovation in Chemistry, Faculty of Science,
Khon Kaen University, Khon Kaen 40002 Thailand
∗
Corresponding author, e-mail: [email protected]
Received 12 Oct 2012
Accepted 6 Dec 2012

ABSTRACT: Benzoin condensation of aromatic aldehydes catalysed by N,N -dimethylbenzimidazolium iodide and NaOH
was performed either in ionic liquid or water or in the absence of solvent. Reusability of the catalyst mixture in all cases
was demonstrated.

KEYWORDS: ionic liquid, water, solvent free condition

INTRODUCTION a Perkin Elmer Spectrum One FT-IR Spectrometer. 1 H

and 13 C NMR spectra were obtained using a VARIAN
As there has been a tendency to avoid hazardous
MERCURY plus (400 MHz FT NMR).
substances in green chemistry, organic reactions car-
rying out in the absence of conventional organic sol- General procedure for benzoin condensation
vents have received more attention. Among various catalysed by N,N -dimethylbenzimidazolium
reactions, the solventless benzoin condensation of iodide (2) and NaOH in [bmim][PF6 ]
benzaldehyde has been reported to proceed efficiently
using sodium methoxide and several imidazolium- To a stirred solution of N,N -dimethylbenzimid-
based ionic liquids as catalyst under microwave irra- azolium iodide (2) (0.218 g, 0.80 mmol) and NaOH
diation 1 . Employing imidazolium-based ionic liquid, (0.032 g, 0.80 mmol) in [bmim][PF6 ] (5 ml) was
1-octyl-3-methylimidazolium bromide, as solvent/- added an aromatic aldehyde (8.00 mmol) at room
catalyst under ultrasonic irradiation also provided a temperature. The temperature was raised to 80 °C
quantitative yield of benzoin 2 . In addition to ionic and the resulting mixture was stirred for 4.5–8 h.
liquids, water is a greener alternative solvent for After completion of the reaction, as indicated by
organic reactions 3, 4 . Accordingly, benzoin condensa- TLC (100% dichloromethane), the reaction mixture
tions catalysed by N,N -dialkylbenzimidazolium salts was extracted with diethyl ether (3 × 80 ml). The
in the presence of amine bases or NaOH in water gives combined organic extract was dried (anh. Na2 SO4 )
α-hydroxy ketones in moderate to excellent yields 5 . and the solvent was removed under reduced pressure.
In our previous work, N,N -dimethylbenzimid- The residue was purified using preparative thin layer
azolium iodide was used as an effective and recyclable chromatography on silica gel with dichloromethane as
catalyst for benzoin condensation 6 . Herein we report eluant.
our extended investigation of greener aspects of ben-
Benzoin condensation of benzaldehyde (1a)
zoin condensation catalysed by N,N -dimethylbenz-
imidazolium iodide and NaOH, i.e., in ionic liquid, Benzoin condensation of benzaldehyde (1a) (0.78 g,
in water, and under solvent free condition. 7.36 mmol) was carried out according to the above
general procedure for 5 h. Purification of the
EXPERIMENTAL SECTION residue gave benzoin (3a) (0.65 g, 83%) and
O-benzoylbenzoin (4a) (0.05 g, 9%).
General Compound 3a was obtained as white crystals; mp
Melting point were determined on Sanyo Gallenkamp 134–136 °C (lit. 7 134–136 °C); IR (KBr) νmax : 3414,
melting point apparatus. IR spectra were recorded on 3057, 3021, 2934, 1674, 1595, 1449, 1266, 1205,

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ScienceAsia 39 (2013) 51

753 cm−1 ; 1 H NMR (CDCl3 , 400 MHz) δ: 7.91 (2H, Compound 3c was obtained as white crystals; mp
d, J = 7.6 Hz, 2- and 6-H), 7.52 (1H, t, J = 7.6 Hz, 87–88 °C (lit. 7 88 °C); IR (KBr) νmax : 3423, 3070,
4-H), 7.39 (2H, t, J = 7.6 Hz, 3- and 5-H), 7.26– 2928, 1674, 1590, 1487, 1401, 1251, 1206, 1091, 977,
7.33 (5H, m, ArH), 5.95 (1H, s, CH), 4.54 (1H, br s, 812 cm−1 ; 1 H NMR (CDCl3 , 400 MHz) δ: 7.75 (2H,
OH); 13 C NMR (CDCl3 ) δ: 76.2, 127.8, 128.6, 128.7, d, J = 8.4 Hz, 2- and 6-H), 7.32 (2H, d, J = 8.4 Hz,
129.1, 133.5, 133.9, 139.0, 198.9. 3- and 5-H), 7.24 (2H, d, J = 8.4 Hz, 30 - and 50 -H),
Compound 4a was obtained as yellow crystals; 7.18 (2H, d, J = 8.4 Hz, 20 - and 60 -H), 5.81 (1H, s,
mp 123–125 °C (lit. 7 125 °C); IR (KBr) νmax : 3069, CH); 13 C NMR (CDCl3 ) δ: 77.3, 129.1, 129.2, 129.4,
2959, 1731, 1695, 1598, 1450, 1280, 1119, 957, 130.4, 131.6, 134.8, 137.2, 140.7, 197.5.
704 cm−1 ; 1 H NMR (CDCl3 , 400 MHz) δ: 8.18 Compound 4c was obtained as yellow crystals;
(2H, d, J = 7.2 Hz, 200 - and 600 -H), 8.05 (2H, d, mp 125–127 °C (lit. 9 127–128 °C); IR (KBr) νmax :
J = 7.6 Hz, 2- and 6-H), 7.41–7.63 (11H, m, ArH), 3090, 2926, 1719, 1698, 1593, 1491, 1366, 1277,
7.15 (1H, s, CH); 13 C NMR (CDCl3 ) δ: 78.0, 128.4, 1092, 961 cm−1 ; 1 H NMR (CDCl3 , 400 MHz) δ: 7.95
128.7, 128.9, 129.2, 129.4, 129.5, 130.0, 133.4, 133.5, (2H, d, J = 8.8 Hz, 200 - and 600 -H), 7.82 (2H, d,
133.8, 134.8, 166.1, 193.8. J = 8.4 Hz, 2- and 6-H), 7.29–7.41 (8H, m, ArH),
6.91 (1H, s, CH); 13 C NMR (CDCl3 ) δ: δ 77.1, 127.5,
Benzoin condensation of p-tolualdehyde (1b) 128.9, 129.2, 129.6, 130.0, 130.1, 131.3, 131.7, 132.7,
Benzoin condensation of p-tolualdehyde (1b) (1.02 g, 135.8, 140.1, 140.4, 165.0, 192.1.
8.50 mmol) was carried out according to the above
general procedure for 8 h. Purification of the Benzoin condensation of furaldehyde (1d)
residue gave 4,40 -dimethylbenzoin (3b) (0.80 g, 78%) Benzoin condensation of furaldehyde (1d) (0.82 g,
and O-(4-methylbenzoyl)-4,40 -dimethylbenzoin (4b) 8.54 mmol) was carried out according to the above
(0.09 g, 12%). general procedure for 4.5 h. Purification of the residue
Compound 3b was obtained as white crystals; gave furoin (3d) (0.51 g, 62%) and O-furoylfuroin
mp 73–75 °C (lit. 8 75–76 °C); IR (KBr) νmax : 3471, (4d) (0.11 g, 18%).
3031, 2920, 1675, 1604, 1512, 1413, 1274, 1095, Compound 3d was obtained as yellow crystals;
779 cm−1 ; 1 H NMR (CDCl3 , 400 MHz) δ: 7.81 (2H, mp 137–139 °C (lit. 7 138–139 °C); IR (KBr) νmax :
d, J = 8.4 Hz, 2- and 6-H), 7.21 (2H, d, J = 8.4 Hz, 3418, 3130, 2964, 1680, 1560, 1466, 1400, 1252,
3- and 5-H), 7.18 (2H, d, J = 8.0 Hz, 20 -H and 60 - 1038, 789, 735 cm−1 ; 1 H NMR (CDCl3 , 400 MHz)
H), 7.11 (2H, d, J = 8.0 Hz, 30 - and 50 -H), 5.89 (1H, δ: 7.61 (1H, s, 5-H), 7.37 (1H, s, 50 -H), 7.24 (1H,
s, CH), 2.35 (3H, s, Ar-CH3 ), 2.28 (3H, s, Ar-CH3 ); d, J = 3.2 Hz, 3-H), 6.53 (1H, d, J = 3.6 Hz, 4-
13
C NMR (CDCl3 ) δ: 21.1, 21.7, 75.8, 127.6, 129.3, H), 6.39 (1H, d, J = 3.2 Hz, 40 -H), 6.34 (1H, d,
129.4, 129.8, 131.0, 136.4, 138.3, 144.9, 198.6. J = 3.2 Hz, 30 -H), 5.79 (1H, s, CH), 4.15 (1H, br s,
Compound 4b was obtained as yellow liquid; IR OH); 13 C NMR (CDCl3 ) δ: 69.2, 109.1, 110.8, 112.6,
(neat) νmax : 2964, 2858, 1725, 1681, 1604, 1413, 120.1, 143.2, 147.7, 149.4, 151.2, 184.4.
1370, 1282, 1173, 1106, 751 cm−1 ; 1 H NMR (CDCl3 , Compound 4d was obtained as brown crystals; mp
400 MHz) δ: 7.92 (2H, d, J = 8.19 Hz, 200 - and 600 - 118–122 °C; IR (KBr) νmax : 3144, 2957, 1727, 1691,
H), 7.82 (2H, d, J = 8.19 Hz, 2- and 6-H), 7.37 1568, 1462, 1396, 1266, 1179, 766 cm−1 ; 1 H NMR
(2H, d, J = 8.19 Hz, 3- and 5-H), 7.17–7.27 (6H, (CDCl3 , 400 MHz) δ: 7.60 (1H, d, J = 0.8 Hz, 500 -
m, ArH) 6.96 (1H, s, CH), 2.33 (3H, s, CH3 ), 2.30 H), 7.59 (1H, d, J = 0.8 Hz, 5-H), 7.47 (1H, d, J =
(3H, s, CH3 ), 2.26 (3H, s, CH3 ); 13 C NMR (CDCl3 ) 0.8 Hz, 50 -H), 7.31 (1H, d, J = 3.6 Hz, 300 -H), 7.30
δ: 21.2, 21.6, 21.7, 77.6, 128.6, 128.9, 129.0, 129.1, (1H, d, J = 2.4 Hz, 3-H), 6.96 (1H, s, CH), 6.57
129.3, 129.7, 129.9, 130.0, 139.2, 145.1, 153.1, 153.2, (1H, d, J = 3.2 Hz, 4-H), 6.51–6.54 (2H, m, 40 - and
165.8, 192.1. 400 -H), 6.40 (1H, dd, J = 3.2 and 1.6 Hz, 30 -H); 13 C
NMR (CDCl3 ) δ: 70.6, 111.1, 112.0, 112.1, 112.5,
Benzoin condensation of p-chlorobenzaldehyde 119.4, 119.5, 143.6, 144.3, 146.3, 147.0, 147.3, 150.2,
(1c) 157.5, 179.3.
Benzoin condensation of p-chlorobenzaldehyde (1c)
(1.04 g, 7.40 mmol) was carried out according to General procedure for benzoin condensation
the above general procedure for 7 h. Purification of catalysed by N,N -dimethylbenzimidazolium
the residue gave 4,40 -dichlorobenzoin (3c) (0.62 g, iodide (2) and NaOH in water
60%) and O-(4-chlorobenzoyl)-4,40 -dichlorobenzoin An aromatic aldehyde (20.0 mmol) was added to
(4c) (0.15 g, 19%). a stirred solution of N,N -dimethylbenzimidazolium

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52 ScienceAsia 39 (2013)

iodide (2) (1.096 g, 4.00 mmol) in 0.2 M NaOH 400 MHz) δ: 7.78 (2H, d, J = 0.8 Hz, 5- and 50 -
(20.0 ml, 4.00 mmol) and the resulting mixture was H), 7.65 (4H, d, J = 4.0 Hz, 3- and 30 -H), 6.64 (2H,
stirred at room temperature for 0.5–8 h. After com- dd, j = 1.6, J = 3.6 Hz, 4- and 40 -H); 13 C NMR
pletion of the reaction, as indicated by TLC (20% (CDCl3 ) δ: 113.1, 124.7, 149.4, 149.5, 176.9.
EtOAc/hexane), the crystalline powder formed was
collected by filtration, washed with water and and General procedure for benzoin condensation
dried in open air. Mixed products was purified using catalysed by N,N -dimethylbenzimidazolium
preparative thin layer chromatography on silica gel iodide (2) and NaOH under solvent free condition
with 20% EtOAc/hexane as eluant. The filtrate was N,N -dimethylbenzimidazolium iodide (2) (0.273 g,
washed with diethyl ether (3 × 30 ml) for reuse. 1.00 mmol) and NaOH (0.040 g, 1.00 mmol) and aro-
matic aldehyde (10.00 mmol) were ground altogether
Benzoin condensation of benzaldehyde (1a) with a pestle and mortar for 10 min and heated at
Benzoin condensation of benzaldehyde(1a) (2.120 g, 80 °C for 4 h. Water (30 ml) was added to the reaction
20.00 mmol) was carried out according to the above mixture and the products extracted with diethyl ether
general procedure for 1 h. Filtration of the crystalline (3 × 30 ml). The combined organic extract was dried
product gave benzoin (3a) (2.05 g, 97%) identical to (anh. Na2 SO4 ) and the solvent was removed under
the previously obtained sample. reduced pressure. The residue was purified using
preparative thin layer chromatography on silica gel
Benzoin condensation of p-tolualdehyde (1b) with 20% EtOAc/hexane as eluant.
Benzoin condensation of p-tolualdehyde (1b) (2.40 g, Benzoin condensation of benzaldehyde (1a)
20.00 mmol) was carried out according to the above
Benzoin condensation of benzaldehyde (1a) (1.12 g,
general procedure for 3 h. Filtration of the crystalline
10.57 mmol) was carried out according to the above
product gave 4,40 -dimethylbenzoin (3b) (2.31 g, 96%)
general procedure. Purification of the residue gave
identical to the previously obtained sample.
benzoin (3a) (0.43 g, 77%), O-benzoylbenzoin (4a)
Benzoin condensation of p-chlorobenzaldehyde (0.06 g, 7%) and benzil (5a) (0.03 g, 3%). Compound
(1c) 3a and compound 4a were identical to the previously
obtained samples.
Benzoin condensation of p-chlorobenzaldehyde (1c) Compound 5a was obtained as yellow crystals;
(2.81 g, 20.00 mmol) was carried out according to mp 95–96 °C (lit. 7 95 °C); IR (KBr) νmax : 3064,
the above general procedure for 3 h. Purification 1660, 1594, 1450, 1325, 1211, 876, 719 cm−1 ; 1 H
of the mixed products gave 4,40 -dichlorobenzoin (3c) NMR (CDCl3 , 400 MHz) δ: 7.98 (4H, d, J = 7.6 Hz,
(0.95 g, 34%) identical with the previously obtained 2-, 20 -, 6- and 60 -H), 7.66 (2H, t, J = 7.6 Hz, 4- and
sample and 4,40 -dichlorobenzil (5c) (1.66 g, 60%). 40 -H), 7.51 (4H, t, J = 7.6 Hz, 3-, 30 -, 5- and 50 -
Compound 5c was obtained as yellow crystals; H); 13 C NMR (CDCl3 ) δ: 129.0, 129.9, 133.0, 134.9,
mp 197–198 °C; IR (KBr) νmax : 3093, 2936, 1660, 194.5.
1587, 1486, 1401, 1316, 1211, 1173, 1096, 834 cm−1 ;
1 Benzoin condensation of p-tolualdehyde (1b)
H NMR (CDCl3 , 400 MHz) δ: 7.85 (4H, d, J =
8.8 Hz, 2-, 20 -, 6- and 60 -H) 7.44 (4H, d, J = 8.8 Hz, Benzoin condensation of p-tolualdehyde (1b) (1.18 g,
3-, 30 -, 5- and 50 -H); 13 C NMR (CDCl3 ) δ: 129.5, 9.83 mmol) was carried out according to the above
131.2, 131.3, 141.9, 192.4. general procedure. Purification of the residue gave
4,40 -dimethylbenzoin (3b) (0.75 g, 64%), O-(4-
Benzoin condensation of furaldehyde (1d) methylbenzoyl)-4,40 -dimethylbenzoin (4b) (0.09 g,
Benzoin condensation of furaldehyde (1d) (1.92 g, 10%), and 4,40 -dimethylbenzil (5b) (0.14 g, 12%).
20.00 mmol) was carried out according to the above Compound 3b and compound 4b were identical to the
general procedure for 0.5 h. Purification of the mixed previously obtained samples.
products gave furoin (3d) (0.06 g, 3%) identical with Compound 5b was obtained as yellow crystals;
the previously obtained sample and furil (5d) (0.42 g, mp 97–99 °C; IR (KBr) νmax : 3047, 2916, 1662,
22%). 1602, 1571, 1328, 1222, 883, 772 cm−1 ; 1 H NMR
Compound 5d was obtained as yellow crystals; (CDCl3 , 400 MHz) δ: 7.86 (4H, d, J = 8.0 Hz, 2-,
mp 163–165 °C (lit. 7 165–166 °C); IR (KBr) νmax : 20 -, 6- and 60 -H), 7.29 (4H, d, J = 8.0 Hz, 3-, 30 -, 5-
3147, 1643, 1533, 1453, 1393, 1279, 1154, 1079, and 50 -H); 13 C NMR (CDCl3 ) δ: 21.8, 129.6, 129.9,
1024, 940, 813, 753 cm−1 ; 1 H NMR (CDCl3 , 130.7, 145.9, 194.4.

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 ScienceAsia 39 (2013) 53

CH3 O
N
O I , NaOH O Ar
N Ar
2 CH3 Ar + O Ar
Ar H Ar
o OH
[bmim][PF6], 80 C O
1a; Ar = 3a; 83% 4a; 9%

1b; Ar = H3C 3b; 78% 4b; 12%

1c; Ar = Cl 3c; 60% 4c; 19%

1d; Ar = 3d; 62% 4d; 18%

O

1
Scheme 1 Scheme I

Benzoin condensation of p-chlorobenzaldehyde with diethyl ether, the ionic liquid containing N,N -di-
(1c) methylbenzimidazolium iodide (2) and NaOH could
Benzoin condensation of p-chlorobenzaldehyde (1c) be reused, even after the third run without loss of
(1.39 g, 9.89 mmol) was carried out according activity, the same products were obtained with no
to the above general procedure. Purification of obvious decrease in their yields.
the residue gave 4,40 -dichlorobenzoin (3c) (0.31 g, Next, we investigated benzoin condensation of
22%), and O-(4-chlorobenzoyl)-4,40 -dichlorobenzoin aromatic aldehydes 1a–d in water. Although it has
(4c) (0.16 g, 15%), and 4,40 -dichlorobenzil (5c) been reported that effective self-condensation of ben-
(0.65 g, 47%) identical to the previously obtained zaldehyde (1a) catalysed by N,N -dialkylbenzimid-
samples. azolium salts required long N -alkyl chain 5 , however,
in our hands this was not the case. Upon stirring either
Benzoin condensation of furaldehyde (1d) benzaldehyde (1a) or p-tolualdehyde (1b) in the aque-
ous solution of 20 mol% of N,N -dimethylbenzimid-
Benzoin condensation of furaldehyde (1d) (1.04 g, azolium iodide (2) in 0.2 M NaOH at room temper-
10.83 mmol) was carried out according to the above ature, self-condensation proceeded efficiently to give
general procedure. Purification of the residue gave the corresponding aroin 3a or 3b as the sole product in
furoin (3d) (0.27 g, 26%), O-furoylfuroin (4d) (0.12 g, nearly quantitative yields as illustrated in Scheme 2.
16%), and furil (5d) (0.41 g, 40%) identical to the Self-condensation of p-chlorobenzaldehyde (1c) and
previously obtained samples. furaldehyde (1d), on the other hand, gave 34%yield
of aroin 3c and 3%yield of aroin 3d along with the
RESULTS AND DISCUSSION corresponding arils 5c and 5d in 59 and 22%yields,
In our recent report,we demonstrated that Stetter re- respectively. Formation of arils 5c and 5d were
actions were accompanied by benzoin condensations resulted from subsequent oxidation of the correspond-
when aromatic aldehydes were treated with ethyl ing aroins 3c and 3d by the mechanism suggested
acrylate in the presence of 20 mol% of N,N -dimethyl- in our previous paper 6 . As has been previously
benzimidazolium iodide (2) and NaOH in ionic liquid, pointed out 11 , the poor overall yield of furoin (3d) and
[bmim][PF6 ], at 80 °C 10 . We, therefore, carried out furil (5d) was owing to the formation of unidentified
benzoin condensation of aromatic aldehydes 1a–d coloured byproduct.
catalysed by 20 mol% of the benzimidazolium salt The aqueous layer, after washing with diethyl
2 and NaOH in [bmim][PF6 ] at 80 °C. As shown in ether, was reused in the self-condensation of benzalde-
Scheme 1, the expected aroins 3a–d were obtained hyde (1b) and p-tolualdehyde (1b) for three times,
as major products together with the aroylaroins 4a– giving in each time similar yields of the corresponding
d as minor products. The aroylaroins 4a–d were aroins 3a and 3b.
resulted from further transformation of the corre- Benzoin condensation catalysed by N,N -di-
sponding aroins 3a–d by the mechanism reported 9 . methylbenzimidazolium iodide (2) and NaOH was
After extraction of the products thus obtained also found to proceed quite efficiently in the absence

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 54 ScienceAsia 39 (2013)

CH3
N
O I , NaOH O O
N
2 CH3 Ar + Ar
Ar H Ar Ar
H2O, rt OH O
1a; Ar = 3a; 97% 5a; 0%

1b; Ar = H3C 3b; 96% 5b; 0%

1c; Ar = Cl 3c; 34% 5c; 59%

1d; Ar = 3d; 3% 5d; 22%

O

1
Scheme 2 Scheme II
CH3 O
N
O I , NaOH O Ar O
N Ar
2 CH3 Ar + O Ar + Ar
Ar H Ar Ar
80 oC OH O O
1a; Ar = 3a; 77% 4a; 7% 5a; 3%

1b; Ar = H3C 3b; 64% 4b; 10% 5b; 12%

1c; Ar = Cl 3c; 22% 4c; 15% 5c; 47%

1d; Ar = 3d; 26% 4d; 16% 5d; 40%

O

1
Scheme 3 Scheme III

of solvent. This was illustrated by heating a grinding ered by the method previously reported 6 .
mixture of an aromatic aldehyde and 20 mol% of
N,N -dimethylbenzimidazolium iodide (2) and NaOH
CONCLUSIONS
at 80 °C for 4 h. As shown in Scheme 3, the con-
densation of aromatic aldehydes 1a–d under solvent Benzoin condensation of aromatic aldehydes catal-
free condition gave the corresponding aroins 3a– ysed by 20 mol% of N,N -dimethylbenzimidazolium
d. In addition to aroins, both aroylaroins and arils, iodide and NaOH could be carried out either in
which occurred when condensations were carried out ionic liquid or water or under solvent free condi-
in [bmim][PF6 ] and in water, respectively, were also tion. Aroylaroins and arils were also obtained as
found under solvent free condition. The amount of minor products. Reusability of [bmim][PF6 ] contain-
aroylaroins 4a–d isolated from solvent free condition ing N,N -dimethylbenzimidazolium iodide and NaOH
were similar to those found from conducting the reac- as well as its corresponding aqueous solution were
tion in [bmim][PF6 ]. Since we also found that aroin demonstrated. The benzimidazolium salt employed
3c could simply and quantitatively transformed to aril under solvent free condition could also be recovered
5d by heating its powder at 80 °C for 4 h, formation of for reuse.
aroils 5a–d under solvent free condition should have
resulted, at least in part, from air oxidation of their Acknowledgements: Financial support from the Centre
corresponding aroins 3a–d at elevated temperature. of Excellence for Innovation in Chemistry (PERCH-CIC),
N,N -dimethylbenzimidazolium iodide (2) em- Office of the Higher Education Commission, Ministry of
ployed under solvent free condition could be recov- Education is gratefully acknowledged.

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ScienceAsia 39 (2013) 55

REFERENCES
1. Estager J, Lévêque JM, Turgis R, Draye M (2006)
Solventless and swift benzoin condensation catalyzed
by 1-alkyl-3-methylimidazolium ionic liquids under
microwave irradiation. J Mol Catal A 256, 261–4.
2. Estager J, Lévêque JM, Turgis R, Draye M (2007) Neat
benzoin condensation in recyclable room-temperature
ionic liquids under ultrasonic activation. Tetrahedron
Lett 48, 755–9.
3. Li CJ (2005) Organic reactions in aqueous media with a
focus on C-C bond formations: A decade update. Chem
Rev 105, 3095–165.
4. Li CJ, Chan TH (2007) Comprehensive Organic Re-
actions in Aqueous Media 2nd edn, Wiley & Sons,
Hoboken.
5. Iwamoto KI, Hamaya M, Hashimoto N, Kimura H,
Suzuki Y, Sato M (2006) Benzoin reaction in water
as an aqueous medium catalyzed by benzimidazolium
salt. Tetrahedron Lett 45, 7175–7.
6. Hahnvajanawong V, Tearavarich R, Theramongkol P
(2005) N,N -dimethylbenzimidazolium iodide: A safe
and recyclable catalyst for conjugate addition of aro-
matic aldehyde to electrophilic double bonds. ACGC
Chem Res Comm 18, 7–10.
7. Buckingham J (1982) Dictionary of Organic Com-
pounds 5th edn, Chapman and Hall, New York.
8. Breslow R (1958) On the mechanism of thiamine
action. IV. Evidence from studies on model systems.
J Am Chem Soc 80, 3719–26.
9. Miyashita A, Matsuda H, Iijima C, Higashino T
(1990) Catalytic action of azolium salts. I. Aroylation
of 4-chloro-1H-pyrazololo[3,4,d]pyrimidines with aro-
matic aldehydes catalyzed by 1,3-dimethylbenzimid-
azolium iodide. Chem Pharmaceut Bull 38, 1147–52.
10. Hahnvajanawong V, Phungpis B, Theramongkol P
(2009) Stetter reaction catalysed by N,N -dimethyl-
benzimidazolium iodide and sodium hydroxide in ionic
liquid. ACGC Chem Res Comm 23, 26–30.
11. Acheson RM (1976) An Introduction to the Chem-
istry of Heterocyclic Compounds. A Wiley-Interscience
Publication, New York. p 145.

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