Natural bio-surfactant for pseudomulticomponent synthesis of 2-aryl-1-aryl methyl-1H-benzimidazoles

Article abstract of DOI:10.2174/1570178614666170710115331

Green chemistry emphasizes the development of environmentally benign chemical processes and technologies. Pseudo-multicomponent synthesis of 2-aryl-1-arylmethyl-1H-benzimidazoles using o-phenylenediamine and aromatic aldehydes is carried out by Br?nsted acid type bio-surfactant as a catalyst. The green features of this method include the use of biodegradable catalyst obtained from renewable resource i.e. Citrus Limonium extract as bio-surfactant type Br?nsted acid, which provides a micellar media for effective cyclocondensation. The critical micellar concentration (cmc) of biosurfactant was determined by conductivity method and visualized by light microscopy measurement. Identity of all pure compounds was ascertained on the basis of FT-IR, ¹H NMR and ¹³C NMR spectroscopic techniques.

Full text of DOI:10.2174/1570178614666170710115331

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Letters in Organic Chemistry, 2018, 15, 57-63
RESEARCH ARTICLE
ISSN: 1570-1786
eISSN: 1875-6255
Natural Bio-surfactant for Pseudomulticomponent Synthesis of 2-Aryl-1-
Impact
Factor:
0.73
aryl Methyl-1H-benzimidazoles
BENTHAM
S
CIENCE
Smita T. Morbale1, Sachin K. Shinde1, Shashikant A. Damate1, Madhukar B. Deshmukh2 and
Suresh S. Patil1,*
1Synthetic Research Laboratory, PG Department of Chemistry, PDVP College, Tasgaon, India; 2Department of Chemis-
try, Shivaji University, Kolhapur, India
Abstract: Green chemistry emphasizes the development of environmentally benign chemical proc-
esses and technologies. Pseudo-multicomponent synthesis of 2-aryl-1-arylmethyl-1H-benzimidazoles
A R T I C L E H I S T O R Y
using o-phenylenediamine and aromatic aldehydes is carried out by Brǿnsted acid type bio-surfactant
as a catalyst. The green features of this method include the use of biodegradable catalyst obtained from
Received: February 24, 2017
renewable resource i.e. Citrus Limonium extract as bio-surfactant type Brǿnsted acid, which provides a
Revised: May 27, 2017
Accepted: June 23, 2017
micellar media for effective cyclocondensation. The critical micellar concentration (cmc) of biosurfac-
DOI:
tant was determined by conductivity method and visualized by light microscopy measurement. Identity
10.2174/1570178614666170710115331
1
of all pure compounds was ascertained on the basis of FT-IR, H NMR and 13C NMR spectroscopic
techniques.
Keywords: Aromatic aldehydes, bio-surfactant, Brǿnsted acid, biodegradable catalyst, Citrus limonium, benzimidazole.
1. INTRODUCTION
components are identical, the reaction is better designated as
pseudo-MCRs. Even though incorporation of two identical
components in the product of a pseudo-MCR exhibits severe
limitation in terms of scope and functional flexibility, these
transformations follow advantage of being very time-
efficient, allowing for the rapid, sometimes spectacular, gen-
eration of molecular complexity. Particularly valuable are
pseudo-MCRs involving successive but distinct and com-
plementary reactivity’s of the same component [22].
Heterocycles play important role for the design and dis-
covery of new compounds of pharmaceutical applications
[1]. Benzimidazoles are important structural motif exhibiting
significant activity against several viruses such as HIV [2],
herpes (HSV-1) [3], RNA [4]. Benzimidazoles act as DNA
minor groove binding agents with antitumor activity [5],
anticancer activity [6]. Their diverse applications comprise
their role as potential angiotensin II inhibitors [7], 5-
lipoxygenase inhibitors for use as novel anti-allergic agents
[8], factor Xa (FXa) inhibitors [9], and ADP-ribose polym-
erase (PARP) inhibitors [10]. Some recently reported meth-
ods regarding benzimidazole synthesis are use of catalyst
such as VO(acac)2 [11], β-cyclodextrin (ZrO2-β-CD) [12],
KOBut [13], Amberlite IR-120 [14], bnmim-HSO4 [15],
MoO3/CeO2-ZrO2 [16], CAN [17], ([Hbim]BF4) [18], L-
Proline [19], SnCl2.2H2O [20], Co-SBA~15 [21]. Although
all these reactions can be efficient and selective but they of-
ten involve expensive reagents, drastic reaction conditions
and tedious work up procedures. Therefore, it was thought
that there is scope for improvement especially towards de-
veloping a green protocol for synthesis of benzimidazoles.
Pseudomulticomponent reactions are multicomponent reac-
tions in which at least one of the two reactants take part in
two or more reaction steps. When two of the three or more
Biosurfactants being natural and promising surfactants
because have certain advantages over chemical surfactants,
such as their lower toxicity, their biodegradable nature, and
their ecological acceptability. Some surfactants are biologi-
cally produced by yeasts or bacteria and are grouped as gly-
colipids, lipopeptides, fatty acids, polymeric and particulate
compounds [23, 24]. One of the fundamental properties of
surfactants is there self-association into organized molecular
structure such as micelles, vesicles, microemulsions, bilay-
ers, membranes and liquid crystals [25]. The simplest class
of association colloids is the micelle. Micellisation character-
istics of surfactant are determined by micellization parame-
ters such as critical micellar concentration(CMC), aggrega-
tion number etc. Combined Brønsted acid surfactant cata-
lysts have also been employed in several organic reactions
[26]. Considering the significance of surfactants, in this
communication, Citrus limonium extract (CLE) was chosen
as catalytic media without using any external promoters,
external acids, ligands, biphasic media and ionic liquids. The
catalytic medium is sourced from the direct extraction of
*Address correspondence to this author at the Synthetic Research Labora-
tory, PG Department of Chemistry, PDVP College, Tasgaon, India;
Tel: 9960734931; E-mail: sanyujapatil@yahoo.com
1875-6255/18 $58.00+.00
© 2018 Bentham Science Publishers

58 Letters in Organic Chemistry, 2018, Vol. 15, No. 1
Morbale et al.
Lemon fruit. A solution containing surfactants presents ap-
preciable changes in physical and chemical properties at the
critical micelle concentration (CMC). CMC is the concentra-
tion of surfactants above which micelles form spontaneously.
Efficient surfactants have very low CMC values, i.e., less
surfactant is required to decrease surface tension [27, 28].
which may form micelles and help to forward the reactions
in proper direction. In addition to this Citrus Limonium ex-
tract (CLE) exhibits acidic pH (2.3). In view of this data and
in continuation of our ongoing research in the development
of green synthetic methodologies [45, 46], we thought that,
this amazing medium may serve as Bronsted acid-type bio-
surfactant, better alternative to chemical surfactants and to
harmful corrosive acids for pseudomulticomponent synthesis
of benzimidazoles.
An intriguing line in the development of eco-friendly
methodologies is being fueled by the basic paradigm shift
from the use of traditional catalysts to natural catalyst. Dif-
ferent natural materials are used as solid support as well as
catalysts in many reactions promoting the formation of final
products. Natural materials such as clays, zeolites, enzymes,
and different plant parts such as fruits, roots, leaves are used
effectively in numerous chemical transformations. The ap-
plications of an aqueous extract of different parts of plants
have witnessed a rapid development. In literature, a number
of organic reactions are reported in which natural catalysts
like clay [29-31], phosphates [32, 33], gold [33] and animal
bone [34] are employed. In recent years, chemical reactions
using plant cell cultures and part of plants as biocatalysts
have received great attention [35-37]. The biocatalytical
transformations using edible plants [38], plant root, [39, 40],
plant tubers [41] and plant leave extract [42] can be applied
in many organic reactions. Fruit extract is also naturally oc-
curring source which was used as biocatalysts in organic
synthesis [43].
2. RESULTS AND DISCUSSION
Fresh Citrus Limonium fruits were cut using knife and
then pieces were pressed manually using domestic presser to
obtain turbid extract. The turbid extract was then filtered
through cotton/muslin cloth and then through filter paper to
remove solid material to get clear extract. The pH of extract
of every batch was measured using pH meter (ProLab 3000
laboratory pH meter) before use and it was found to be 2.1-
2.3. The prepared catalyst was stored several days at 5oC and
used for the synthesis of benzimidazole derivatives.
When o-phenylenediamine (1 mmol) 1 and various aro-
matic aldehydes (2 mmol) 2 were treated by employing CLE
catalyst in ethanol at different temperatures (Scheme 1), both
expected products viz. 2-aryl-1H-benzimidazoles 3 and 2-
aryl-1-arylmethyl-1H-benzimidazoles 4 were obtained de-
pending on the reaction temperature and solvent employed.
The best overall yields and selectivity’s were obtained in
ethanol at 80oC temperature, in which only N-substituted
benzimidazoles 4 were produced.
The main objectives of this protocol are to develop an
efficient synthetic process for the facile cyclocondensation of
o-phenylenediamine and aldehydes under mild reaction con-
ditions. The operational simplicity of the process without the
need for special handling is also noteworthy. This new pro-
tocol for benzimidazoles can be accomplished with excellent
yields for a broad range of aromatic aldehydes.
Initially, to optimize the reaction conditions, we exam-
ined the condensation of o-phenylenediamine (1 mmol) 1
and benzaldehyde (2 mmol) 2 as a model reaction in the
presence of CLE (0.5 mL) at room temperature in the ab-
sence of Co-surfactant. Surprisingly, contrary to our expecta-
tion, only 2-phenyl-1H-benzimidazole 3a was obtained in 20
Phytochemical study showed the presence of limonoids,
flavonoids and catechins [44] (Fig. 1) present in lemon
OH
OH
OH
O
O
O
HO
O
HO
OH
O
O
O
O
O
O
R
OH
OH
(a)
(b)
(c)
Hydrophilic
Hydrophobic
Fig. (1). Phytochemicals producing micelles (a) Flavonoids, (b) Limonoids and (c) Catechin.
CHO
NH2
CLE/Ethanol (3:5 v/v)
N
N
+
80oC
+
NH2
R
R
N
R
N
H
1
2
R
3
4
Scheme (1). Synthesis of benzimidazoles.

Natural Bio-surfactant for Pseudomulticomponent
Letters in Organic Chemistry, 2018, Vol. 15, No. 1 59
Table 1. Optimization of reaction parameters for 2-aryl-1-aryl methyl-1H-benzimidazole 4a formationa.
Yieldb (%)
Amount of
Catalyst (mL)
Catalyst:
Co-surfactant Ratio
Entry
Co-surfactant 5 (mL)
Temp. (oC)
Time (min)
3a
4a
1
2
0.5
3.0
5.0
10.0
5.0
5.0
5.0
5.0
5.0
2.0
3.0
7.0
10.0
15.0
5.0
--
--
--
--
--
RT
RT
RT
RT
80
80
80
80
80
80
80
80
80
80
RT
80
180
180
180
180
180
30
20
27
30
33
31
00
00
00
00
00
00
00
00
00
36
00
00
00
00
00
60
81
90
86
82
51
92
86
70
49
00
00
3
-
-
4
-
-
5
--
--
6
Methanol
Ethanol
Iso-propanol
t-butanol
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
1:1
1:1
1:1
1:1
2:5
3:5
7:5
2:1
3:1
1:1
-
7
30
8
30
9
30
10
11
12
13
14
15
16
45
45
45
45
45
180
180
bReaction condition: Aromatic aldehyde (2 mmol), o-phenylelediamine (1 mmol) isolated yield.
% yield (Table 1, entry 1). Expected N-substituted derivative
1-benzyl-2-phenyl-1H-benzo[d]imidazole 4a was not ob-
tained. On the increase in the catalytic amount from 0.5 to 10
mL, slight improvement was observed in the yield of 3a
without formation of any traces of 4a (Table 1, entry 2-4).
examined; the result observed was viscous reaction system
and no product formation which indicates that the role of
bio-surfactant is decisive for benzimidazoles formation (Ta-
ble 1, entry 16).
Initially on stirring, the reaction mixture turned to yellow
turbid emulsion, (Fig. 2a) which implies that there is the
formation of micelles or micelle-like colloidal aggregates
which was visualized through an optical microscope (Fig.
2b). CMC is the narrow concentration range over which am-
phiplic or surfactant solution shows an abrupt change in
physical property such as electrical conductivity, surface
tension, osmotic pressure, density, light scattering, or refrac-
tive index [47]. The aggregation of organic ingredients from
CLE during reaction condition results in the semi-ordered
structure of micelles protruding into aqueous phase whereas
the hydrophobic parts are brought to close proximity in the
core of the aggregate excluding water. When organic com-
pounds are introduced in an alcoholic micellar solution, hy-
drophobic interactions will cause binding of these com-
pounds to the micelles and get collected in the core of mi-
celle where the reaction occurs more easily. This further con-
firmed that, the catalyst does not simply provide the acidic
medium to activate the substrate molecules but also helps to
aggregate all the reactants into micelles.
We continued our efforts for improvement in the result
when model reactants were allowed to react at elevated tem-
perature (80oC) without co-surfactant, in the presence of 5
mL CLE, after 3 h, surprisingly both the products 3a and 4a
were obtained (first observed on TLC) in 31 and 60 % yield
respectively (Table 1, entry 5). Since co-surfactnt properties
play a crucial role in organic synthesis, the effect of co-
surfactnt was studied for the synthesis of benzimidazoles.
(Table 1, entry 6-9). It was found that ethanol was a more
efficient co-surfactant for the present transformation (Table
1, entry 7). The results led us to examine co-surfactant effect
for this condensation.
Ethanol at higher temperature worked as a co-surfactant
leading to selective synthesis of 4a along with enhanced
product yield. It was also noticed that the condensation using
co-surfactant proceeded rapidly and was superior to the re-
ported procedures with respect to the reaction time and yield
of product. We also optimized the surfactant:co-surfactant
ratio for model reaction by changing amount CLE (Table 1,
entry 10-14). The result showed that CLE:Ethanol ratio at
just above cmc (33 %) is a suitable medium for smooth con-
version of reactant to the product with respect to time and
yield (Table 1, entry 11). At ambient temperature with same
reaction conditions, 36 % yield of 3a was obtained (Table 1,
entry 15). Moreover, the catalyst-free condition was also
Electrical conductivity method was employed to deter-
mine the critical micelle concentration (cmc) and it was
found to be 33 % v/v (Fig. 3). This helped us to maintain
better surfactant:co-surfactant ratio for this cyclocondensa-
tion.

60 Letters in Organic Chemistry, 2018, Vol. 15, No. 1
Morbale et al.
(ii)
(a)
(i)
(iii)
(i)
(ii)
(b)
Fig. (2). (a) Reaction mixtures at different stages, (i) at starting: 0 min, (ii) after: 10 min, (iii) after completion of reaction: 30 min; (b) Optical
micrograph of reaction mixture, (i) normal view [40x magnification], (ii) magnified view [100x magnification].
Fig. (3). Critical micelle concentration (cmc) obtained from plot of specific conductance against percentage composition of bio-surfactant in
ethanol.
CHO
R
N
N
NH2
+
R
NH2
R
Hydrophobic interior
Hydrophilic exterior
Fig. (4). Mechanistic picture of role of micellae for Benzimidazole formation.
The micelle formation occurs above CMC at which the
monomers undergo self-assembly to form aggregate in the
solution. This caused the solution converted from true solu-
tion to become a colloidal system. The micellar solution is
known as a colloidal dispersion (association colloid) of or-
ganized surfactant molecules. The micelle formed in the so-
lution is spherical structure which the hydrophilic head
group was exposed to the solution while the hydrophobic
tails were faced toward the interior of the micelle structure
(Fig. 4).

Natural Bio-surfactant for Pseudomulticomponent
Letters in Organic Chemistry, 2018, Vol. 15, No. 1 61
Table 2. Recyclable properties of CLE catalyst.
Run
1
2
3
4
5
% Yield
92
92
90
85
82
Table 3. CLE catalyzed synthesis of 2-aryl-1-aryl methyl-1H-benzimidazole derivativesa.
Sr. No.
Aldehydes
Product
Time (min)
Yieldb (%)
1
2
C6H5
4-ClC6H4
4a
4b
4c
4d
4e
4f
30
25
35
40
35
20
30
25
40
45
40
40
45
45
45
20
25
92
92
88
84
89
94
90
92
86
86
90
90
84
81
84
92
91
3
4-OHC6H4
4
4-CH3C6H4
5
4-OCH3C6H4
4-NO2C6H4
6
7
2-ClC6H4
4g
4h
4i
8
2-NO2C6H4
9
2-OHC6H4
10
11
12
13
14
15
16
17
4-(Me)2NC6H4
2-OH,5-NO2 C6H3
4-FC6H4
4j
4k
4l
5-OC2H5,4-OHC6H3
2, 5-OCH3C6H3
4-OH,5-OCH3C6H3
3-Br,4-FC6H3
2-F,4-BrC6H3
4m
4n
4o
4p
4q
18
4r
50
83
86
O
19
4s
45
S
aReaction conditions: o-phenylenediamine (1 mmol), aromatic aldehyde (2mmol), bio-surfactant (3 mL), ethanol (5 mL), 80oC temperature.
bIsolated yield based on o-phenylenediamine.
Co-surfactants are weakly amphiphilic molecules, which
are assumed to concentrate in the surfactant layer of the ag-
gregates formed by the primary surfactant. Due to their weak
amphiphilic character, co-surfactants alone do not form ag-
gregates, but they strongly support aggregation of the pri-
mary surfactant [48]. Alcohols being a good co-surfactant
when used with surfactants, it can lower the surface tension
and reduce the emulsion size. Alcoholic -OH head group can
fit into the gap between the surfactant molecules providing
bonus steric repulsion. Due to reduction in micellar size,
there is more aggregation of substrate molecules, enhancing
the solublisation effect for better conversion of reactants into
products. Short chain co-surfactant molecules like ethanol
can more easily accommodate themselves among the surfac-
tant molecules at the droplet interface thereby releasing this
bending stress [49]. Both the surfactant property and strong
Bronsted acidity of CLE are essential to promote the reaction
efficiency.
ate work-up (see experimental), lemon extract was treated
with activated charcoal and, after filtration, was used for re-
synthesis of 4a. Synthesis was performed five times and the
influence of recycling lemon extract on yields of 4a is shown
(Table 2). As can be seen, lemon extract can be reused five
times without any appreciable loss in catalytic activity,
clearly proving its recyclability and reusability.
In order to evaluate the generality of the process, scope
and limitation of the catalysts, several diversified examples
illustrating the present method for the 2-aryl-1-aryl methyl-
1H-benzimidazoles 4 were examined. The reaction of o-
phenylenediamine with various aromatic aldehydes bearing
electron withdrawing groups or electron releasing groups
was carried out in optimized reaction conditions. The prod-
uct obtained were good to excellent yield, which are nor-
mally observed under the influence of strong acids. The results
obtained in the current method are illustrated in Table 3. From
results, it was revealed that aldehydes having electron with-
drawing groups reacted very well at faster rate compared
with aromatic aldehydes substituted with electron releasing
In order to investigate the recyclability and reusability of
lemon extract, we synthesized compound 4a, after appropri-

62 Letters in Organic Chemistry, 2018, Vol. 15, No. 1
Morbale et al.
CHO
NH4OAC
O
+
O
CLE/Ethanol (3:5 v/v)
80oC
N
+
N
H
R
R
6
7
7(a-j)
5
Scheme (2). Synthesis of 2, 4, 5-trisubstituted imidazole derivatives 7.
Table 4. CLE catalyzed synthesis of 2, 4, 5-trisubstituted imidazole derivativesa.
Sr. No.
Aldehydes
Producta
Time (min)
Yieldb(%)
1
2
C6H5
4-ClC6H4
7a
7b
7c
7d
7e
7f
40
25
40
40
25
30
30
40
45
50
90
92
84
82
90
86
83
84
81
84
3
4-OHC6H4
4
4-MeC6H4
5
4-NO2C6H4
4-MeOC6H4
4-(Me)2NC6H4
2-OH,3-OMe C6H3
2,5-(OMe)2 C6H3
4-FC6H4
6
7
7g
7h
7i
8
9
10
7j
aReaction conditions: Benzil (1 mmol), aromatic aldehyde (1 mmol), ammonium acetate (2 mmol) bio-surfactant (3 mL), ethanol (5 mL), 80oC temperature.
bIsolated yield based on benzil.
groups. A heterocyclic aromatic aldehyde such as 2-furaldehyde
and 2-thiophine aldehyde could also react efficiently to af-
ford the corresponding benzimidazole derivatives with a
good yield (Table 3, entry 18, 19).
ture were separated by filtration and washed with 10 mL of
cold water by twice to remove the catalyst and dried in vac-
uum. The pure product was obtained by recrystallization
from 96% ethyl alcohol and their identity was ascertained on
1
the basis of FT-IR, H NMR and 13C NMR spectroscopic
Based on recently reported method for the synthesis of
trisubstituted imidazoles from simple and easily available
starting materials under much milder reaction conditions [50],
we extended present protocol for the synthesis of highly
substituted imidazoles by performing one-pot condensation
(Scheme 2) in CLE:EtOH (3:5, v/v) at 80oC. The feasibility
of the reaction is tested on various aromatic aldehydes with
1,2-dicarbonyl compound (benzil) and ammonium acetate.
The results obtained are in good yield and are summarized in
Table 4. In all cases, the products are isolated in stipulated
techniques. The physical and spectroscopic data are in con-
sistent with the proposed structure and is in harmony with
the literature values. Similar procedure was applied for the
synthesis of 2, 4, 5-trisubstituted imidazole derivatives in
which aromatic aldehydes, benzil and ammonium acetate were
employed as a substrate in 1:1:2 proportion respectively.
CONCLUSION
1
time and are characterized by their IR, H NMR,13C NMR
To the best of our knowledge, this is the first report of an
environmental-friendly protocol for benzimidazole cyclo-
condensation reaction carried out in CLE as bio-surfactant
type Brǿnsted acid. In the present scheme, we project biosur-
factant nature of catalyst obtained from renewable resource
which provides green, efficient and eco-compatible process
for the selective pseudomulticomponentsynthesis of 2-aryl-1-
arylmethyl-1H-benzimidazoles by one-pot reaction. The use
of readily available and biodegradable catalyst in replace-
ment to hazardous acids and toxic chemical surfactants is a
promising alternative for the organic reactions. This method
also offers to overcome the problem of obtaining two possi-
ble products in reaction mixture for benzimidazole synthesis
by varying the temperature conditions.
spectroscopy.
3. EXPERIMENTAL
3.1. General Procedure for the Synthesis of 2-aryl-1-
arylmethyl-1H-benzimidazoles 4(a-s)
To the reaction mixture containing o-phenylenediamine
(1 mmol) 1, aromatic aldehyde (2 mmol) 2, freshly prepared
CLE (3 mL) and ethanol (5 mL) was added. Then the reac-
tion mixture was stirred at 80oC on preheated oil bath for
appropriate time mentioned in Table 2. The progress of reac-
tion was monitored by TLC (n-hexane:ethyl acetate, 3:1).
The crude product 4 obtained after cooling at room tempera-

Natural Bio-surfactant for Pseudomulticomponent
Letters in Organic Chemistry, 2018, Vol. 15, No. 1 63
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Duan, L.P.; Li, Q.; Wu, N.B.; Xu, D.F.; Zhang, H.B. Chin. Chem.
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