American Journal of Organic Chemistry 2012, 2(2): 1-6
DOI: 10.5923/j.ajoc.20120202.01
SBSA as a New and Efficient Catalyst for the One-Pot
Green Synthesis of Benzimidazole Derivatives
at Room Temperature
Sami Sajjadifar
*
, Seyed Ahmad Mirshokraie, Nematollah Javaherneshan, Omid Louie
Department of Chemistry, Payame Noor University, P. O. BOX 19395-4697, Tehran, Iran
Abstract silica boron sulfonic acid (SBSA) was easily prepared and used as a new and efficient solid acid catalyst for
the synthesis of benzimidazole derivatives with high isolated yields. Various substituted benzimidazoles were synthesized
by a combination of o-phenylenediamines and aldehydes in the presence of boron sulfonic acid in with good yields in water
and under a mild reaction conditions. This method is also applicable for precursors such as: aromatic and unsaturated alde-
hydes and o-phenylenediamines.
Keywords Silica Boron Sulfonic Acid, SBSA, Solid Acid, Benzimidazole Synthesis, Drugs, Green Synthesis
1. Introduction
Benzimidazole moieties are classified under several
classes of drugs[1], based on the possible substitution at
different positions of the benzimidazole nucleus. Benzimi-
dazole derivatives exhibit significant activity against several
viruses such as HIV, human cytomegalovirus (HCMV)[2],
herpes (HSV-1)[3], RNA[4] and influenza[4]. Furthermore
they have been also used to act as topoisomerase inhibi-
tors[6], selective neuropeptide YY1 receptor antagonists[7],
angiotensin II inhibitors[8], potential antitumor agents[9]
and smooth muscle cell proliferation inhibitors[10]. In addi-
tion benzimidazoles are very important precursors in or-
ganic synthesis. Vitamin B
12
constitutes a milestone in the
chemistry of benzimidazoles. Bisbenzimidazole is DNA-
minor grove binding agents possessing anti-tumour activ-
ity[11].
A number of methods have been reported for the synthe-
sis of benzimidazoles such as the condensation of
o-aryldiamines and aldehyde in refluxing nitrobenzene[12].
The coupling of phenylenediamines and carboxylic acids
[13] or their derivatives (nitriles, imidates, or orthoest-
ers)[14], which often requires strong acidic conditions[15],
and sometimes combines with very high temperatures or
microwave irradiation[16]. The other route involves a
two-step procedure that includes the oxidative cyclo- dehy-
drogenation of Schiff bases, which are often generated
from the condensation of o - phenylenediamines and
* Corresponding author:
ss_sajjadifar@yahoo.com (Sami Sajjadifar)
Published online at http://journal.sapub.org/ajoc
Copyright © 2012 Scientific & Academic Publishing. All Rights Reserved
aldehydes. Dir - condensation of o-aryldiamines and alde-
hydes is not a good synthetic reaction, as it is well known to
yield a complex mixture, being 1,2-disubstituted benzimi-
dazoles, the bis anil and dihydrobenzimidazoles as the main
side products[17]. However, the addition of transition metal,
namely copper (II) acetate[18], mercury oxide[19] or lead
tetracetate[20] allows a partial selective synthesis of ben-
zimidazoles. In recent years, solvent-free synthesis of ben-
zimidazoles under microwave irradiation using
Yb(OTf)
3
[21], KSF clay[22], PPA[23], Na
2
SO
4
[24], K-10
clay[25], metal halide supported alumina[26] and solid
support[27] have been reported. Various oxidative and
catalytic reagents such as sulfamic acid[28], I
2
[29],
DDQ[30], Air[31], Oxone[32], FeCl
3
·6H
2
O[33], In(OTf)
3
[34], Yb(OTf)
3
[35], Sc(OTf)
3
[36], KHSO
4
[37], IL[38], Ni-
trobenzene[39] , 1,4 – benzo quinine [40], tetracyano eth-
ylene [41], benzofuroxan [42], MnO
2
[43], Pb(OAc)
4
[44],
NaHSO
3
[45], Na
2
S
2
O
5
[46], DMP[47], NH
4
VO
3
[48], have
been employed. Benzimidazole derivatives can be synth-
sised by another catalysts such as CAN [49], p-TsOH[50],
BE
3
.OEt
2
[51], KHSO
4
[52], CuPy
2
Cl
2
[53], polyphosphoric
acid[54], mineral acids[55], boric acid [56], p-TSA [57],
Dowex 50W [58], SSA [59], solid acid scolecite [60], YCl
3
[61], Zn(OAc)
2
[62], N- halosuccinamide (X = Cl, Br, I)
[63], Yb(OTf)
3
[64], PEG-100 [65], (NH
4
)H
2
PW
12
O
40
[66],
bismuth chloride[67], mercury chloride[68], Ionic liq-
uids[69], AMA[70], TBAF[71], H
2
O
2
/ SiO
2
-FeCl
3
[72],
HBF
4
-SiO
2
[73] and MoO
3
/CeO
2
-ZrO
2
[74]. Unfortunately,
many of these processes suffer some limitations, such as
drastic reaction conditions, low yields, tedious work up
procedures and co-occurrence of several side reactions. In
this article, we report a simple and efficient method for the
synthesis of benzimidazole derivatives using SBSA as a