Anhydrous FePo4: A green and cost-effective catalyst for the one-pot three component synthesis of 2,4,5-triarylated imidazoles

Article abstract of DOI:10.3987/COM-10-12019

A simple and efficient synthesis of 2,4,5-triarylated imidazoles is achieved by three-component cyclocondensation of benzil and benzoin, aryl aldehyde and ammonium acetate using FePO₄ as a catalyst in refluxing ethanol. The key advantages of this process are high yields, cost effectiveness of catalyst, easy work-up, purification of products by non-chromatographic methods and developing of a new derivative of 2,4,5-triarylated imidazole. The Japan Institute of Heterocyclic Chemistry.

Full text of DOI:10.3987/COM-10-12019

HETEROCYCLES, Vol. 81, No. 10, 2010
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HETEROCYCLES, Vol. 81, No. 10, 2010, pp. 2313 - 2321. © The Japan Institute of Heterocyclic Chemistry
Received, 13th July, 2010, Accepted, 26th August, 2010, Published online, 26th August, 2010
DOI: 10.3987/COM-10-12019
ANHYDROUS FePO4: A GREEN AND COST-EFFECTIVE CATALYST
FOR THE ONE-POT THREE COMPONENT SYNTHESIS OF 2, 4, 5-
TRIARYLATED IMIDAZOLES
Farahnaz K. Behbahani,* Talaye Yektanezhad, and Afshin R. Khorrami
Department of Chemistry, School of sciences, Islamic Azad University Karaj
Branch, Karaj, Iran
Abstract – A simple and efficient synthesis of 2,4,5-triarylated imidazoles is
achieved by three-component cyclocondensation of benzil and benzoin, aryl aldehyde
and ammonium acetate using FePO4 as a catalyst in refluxing ethanol. The key
advantages of this process are high yields, cost effectiveness of catalyst, easy work-up,
purification of products by non-chromatographic methods and developing of a new
derivative of 2,4,5-triarylated imidazole.
INTRODUCTION
Imidazoles are an important class of heterocycles being the core fragment of different natural products
and biological systems. Compounds containing imidazole moiety have many pharmacological
properties and play important roles in biochemical processes 1 such as viz. histidine, histamine and biotin,
an active component in several drug molecules 2 and pesticides 3 have received a lot of attention in recent
years. Also different substituted imidazoles show a broad range of biological activities such as
anti-inflammatory activity,4 anti-allergic activity,5 and analgesic activity.6 In addition, many of the
substituted diaryl imidazoles are known as potential inhibitors of the p38 MAP kinase.7 Among these
imidazoles, 2, 4, 5-triphenylimidazoles can be used as light-sensitive materials in photography, fungicides
and herbicides, plant growth regulators,8 and other type of therapeutic agents. Appropriately substituted
imidazoles are extensively used as glucagons receptors9 and CB1 cannabinoid receptor antagonists,10
modulators of P-glycoprotein (P-gp)-mediated multidrug resistance (MDR),11 antibacterial,12 and
antitumor13 agents.
The first synthesis of the imidazole core was reported in 1882 by Radziszewski and Jaap, starting from
1,2-dicarbonyl compounds, aldehydes and ammonia, to obtain 2,4,5-triphenylimidazole.14 The great
biological importance of the imidazole nucleus over the years has raised the development of new and
improved methodologies.

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HETEROCYCLES, Vol. 81, No. 10, 2010
Varying the methods reported to synthesize imidazoles such as hetero-Cope rearrangement,15 four-
component condensation of aryl glyoxals, primary amines, carboxylic acids and isocyanides on Wang
resin,16 reaction of N-(2-oxo)-amides with ammonium trifluroacetate,17 1,2-aminoalcohols in the presence
of PCl5,18 diketones, aldehyde, amine and ammonium acetate in phosphoric acid,19 in acetic acid,20
organo catalyst in acetic acid21 as well as H2SO422 and DMSO.23
Also several micro-wave (MW) assisted syntheses of imidazoles from 1, 2-diketones and aldehydes in the
presence of a variety of catalysts have been reported. These include MW/silica-gel,24 MW/Al2O3,25
MW/acetic acid,26 in DMF. The condensation of α-hydroxyl ketones with aldehydes and ammonium
acetate on solid supported silica gel or alumina in the presence of MW.27
Recently, the synthesis of these imidazoles has been catalyzed by silica gel or Zeolite HY,28 molecular
33
iodine,29 H3PW12O40, 30 Yb(OTf)3,31 NdCl3,32 LaCl3, FeCl3,34 AlCl3,35 Al2O3,36 NiCl2,37 [HBim]BF4,38
InCl3·3H2O,39 ionic liquid,40 silica sulfuric acid,41 ytterbium perfluorooctanesulfonate (Yb(OPf)3),42
Zr(acac)4,43 and tetrabutylammonium bromide.44
Although these methods possess a lot of alternative, the reactions suffer from low yields, longer reaction
times, use of expensive reagents, use of toxic solvents and agents associated with a mixture of products
and lack of generality, thus they were not suitable for, or were not applied for, the synthesis of
structurally diverse imidazoles.
In addition to cases mentioned above, FePO4 is cheap, safe, and available reagent45 that has also been
employed for the selective oxidation of CH4 to CH3OH46 and benzene to phenol47 and one-pot synthesis
of dihydropyrimidinones and thiones48 as a catalyst. Therefore, in connection with our research49 for the
development of simple and efficient methods for the synthesis of various heterocyclic compounds herein,
we present iron (III) phosphate as a green, reusable, recyclable, safe-environmentally, inexpensive and
commercially catalyst for the synthesis of 2,4,5-triaryl-1H-imidazoles ( Scheme 1).
O
O
O
H
N
NH4OAc, FePO4
EtOH, reflux
+
N
R
R
1
3
4(a-j)
or
O
OH
2
Scheme 1. Synthesis of 2, 4, 5-triarylimidazoles using FePO4

HETEROCYCLES, Vol. 81, No. 10, 2010
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RESULTS AND DISCUSSION
The reaction conditions (solvent, reaction time, and catalytic amount of catalyst) were studied to
standardize this procedure. The results on the synthesis of 2,4,5-triphenyl-1H-imidazole from the reaction
of benzil, benzaldehyde, ammonium acetate, water and ethanol using FePO4 are summerized in Table 1.
Of solvents including ethanol, water, and ethanol/water, ethanol proved to be the best in terms of yield.
Thus in present study has been used only ethanol, which is relatively benign organic solvent. We found
that, the heterocyclization reaction is facilitated by increasing the temperature, so the reaction proceeded
in ethanol under reflux condition to give a high yield at a relative short reaction time.
Table 1. Effect of varying the solvent and the amounts of FePO4 on the yields and
reaction times of synthesis of 2,4,5-triphenyl-1H-imidazole using 1.0 mmol each of
benzil and benzaldehyde under reflux conditions 4a
Solvent
FePO4 (mol %)
Time (h)
Yield %
H2O
15
15
15
15
10
7
24
5
10
EtOH- H2O (1:1)
EtOH- H2O (3:1)
EtOH
75
4
80
2
94
EtOH
2
94
EtOH
3
85
EtOH
5
4
80
The amount of NH4OAc required for reaction and to increase the yield of 2,4,5-triphenyl-1H-imidazole
was investigated, and the results are summarized in Table 2. As shown, the optimum amount of NH4OAc
was 5 mmol in the presence of 1 mmol each of benzaldehyde and benzil.
Table 2. Effect of varying the amounts of NH4OAc on the yields of 2,4,5-triphenyl-1H-imidazole
Solvent
EtOH
EtOH
EtOH
EtOH
NH4OAc (mmol)
Time (h)
Yield %
1.2
2.5
4.0
5.0
48
48
10
2.0
70
70
80
94
To illustrate the need of catalyst, FePO4, for this reaction, experiments were conducted in which the
model reaction of was studied in the absence of catalyst. The reaction was not completed even after 24 h.
Undoubtedly, the catalyst is an efficient component of the reaction. The amount of the catalyst required
for the reaction and to increase the yield of 2,4,5-triphenyl-1H-imidazole was investigated, and the results
are summarized in Table 1. Results clearly indicate that 10 mol% of FePO4 is sufficient to catalyze the

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HETEROCYCLES, Vol. 81, No. 10, 2010
cyclocondensation reaction.
In order to show the merits of the present work, the variety of aldehydes with electron-donating and
electron-withdrawing groups on the aromatic ring, benzil, benzoin, ammonium acetate and FePO4 in
ethanol were subjected for synthesis of 2,4,5-triarylated-1H-imidazole. We found that for aldehydes
bearing either electron-releasing or electron withdrawing substituents in the ortho, meta or para positions,
the reaction proceeded very efficiently in all cases (Table 3).
1, 2-diketones (like benzil) are usually prepared from the α-hydroxy ketones (like benzoin) catalyzed by
various oxidants. Some of these catalysts are toxic, costly and also required the tedious experimental
procedures.50 Aimed to evaluate direct oxidation condensation reaction, the synthesis of 2,4,5-triphenyl-
1H-imidazole was studied using benzoin (Table 3: entry 1). Surprisingly, using the similar reaction
conditions, 2,4,5-triphenyl-1H-imidazole was isolated in 92% yield. Encouraged by this result, we
extended the methodology for synthesis of various 2,4,5-triaryl-1H-imidazoles using benzoin and various
aromatic aldehydes. The yields obtained were in the range of 72 to 95%.
The overall greenness of this reaction was high as minimum amount of environmentally benign ethanol
and FePO4 were used during the course of reaction. Moreover, it is important to note that in all cases,
after completion of the reaction FePO4 filtrated off and reused for another run (Table 4). Imidazoles were
also precipitated on dilution of the reaction mixture with water and were isolated by a simple filtration.
The dried product that obtained showed a single spot on TLC and was pure enough for all practical
purposes. The other advantages of this research are synthesis of (E)-4,5-diphenyl-2-styryl-1H-imidazole
and 2-(3,5-dichlorophenyl)-4,5-diphenyl-1H-imidazole for first time as a new imidazole derivatives
(Table 3: entries 4, 6). We are willing to survey their biological properties in future.
A probable mechanism for the synthesis may be postulated as shown below (Scheme 2). FePO4 is Lewis
acid because of the hard character of its metal cation, so that it can activate the carbonyl group (C=O) to
decrease the energy of transition state. It is highly probable that the carboxyl groups of benzil 1 and
aldehydes 3 have to be activated which occurs when the carbonyl oxygen is coordinated by FePO4. Then
nucleophilic attack of the nitrogen of ammonia obtained from NH4OAc on the activated carbonyl group,
resulted in formation of aryl aldimine 6 and α-imino ketone 5, and it followed by the nucleophilic attack
of the in situ generated imine 6 to carbonyl of aryl aldimine 3, giving the intermediate 7. Their subsequent
intramolecular interaction leads to cyclization and eventually to the formation of intermediate 8, which
dehydrates to the trisubstituted imidazoles 4.
CONCLUSION
In summary, this manuscript describes a simple, convenient, green, easy and efficient method to prepare a
variety of triaryl-substituted imidazoles in the presence of catalytic amount of FePO4. The catalytic

HETEROCYCLES, Vol. 81, No. 10, 2010
2317
activity of FePO4 is remarkable and the use of low cost, commercially available FePO4 as catalyst for the
synthesis of triaryl imidazoles in excellent yields is also significant under the aspect of environmentally
benign processes. The advantages, such as shorter reaction times, product yields, the easy procedure to
carry out the reaction makes the inexpensive and commercially available FePO4 as a powerful catalyst for
the synthesis of imidazoles.
Table 3. Synthesis 2, 4, 5-triaryl-1H-imidazoles using benzil or benzoin, ammonium acetate, aromatic and aliphatic
aldehydes, and 10 mol% FePO4
Entry
ArCHO
Product
Time (h)
Yield (%)
Mp (˚C)
benzil 1 benzoin 2
benzyl 1 benzoin 2
Found
Reported
274-275 27515
H
N
1
C6H5CHO
3a
3b
2.0
2.5
94
92
Ph
Ph
Ph
Ph
Ph
N
4a
4b
2
3
3-nitro-C6H4CHO
NO2
3.0
3.5
96
93
95
316-317 314-31515
H
N
N
3,4-diMeO-C6H3CHO
3c
2.5
3.0
90
93
216-217 220-22130
OMe
OMe
Ph
H
N
N
Ph
Ph
4c
4d
4e
4
5
6
trans-C6H5CH=CHCHO 3d
H
N
2
2.5
5.0
4.5
95
85
92
272-273
---
Ph
N
Ph
Ph
259-260 261-26315
H
N
4-Cl-C6H4CHO
3e
3f
4.5
4.0
81
Cl
N
Ph
Ph
3,5-diCl-C6H4CHO
90
172-173
---
Cl
Cl
H
N
N
Ph
Ph
4f
177-178 176-17751
249-250 257-25830
H
N
7
8
2,4-diCl-C6H4CHO
3g
6.0
3.0
6.5
3.5
74
88
72
85
85
Cl
N
Ph
Ph
Cl
4g
4h
H
N
4-N,N-diMe-C6H4CHO 3h
NMe2
N
Ph
Ph
237-238 248-24952
182-183 196-19715
H
N
9
4-Br-C6H4CHO
3i
3j
3.0
3.5
3.5
4.0
87
94
Br
N
Ph
Ph
4i
4j
H
N
10
4-nitro-C6H4CHO
91
NO2
N
Ph
Table 4. Recycling and reusing of the catalyst for the synthesis of 2-(4-chlorophenyl)- 4,5-diphenyl-1H-imidazole has
been shown
Entry
Aldehyde
Yield% [Time(h)]
Benzil
85[4.5]
83[4.5]
83[4.5]
Benzoin
81[5.0]
80[5.0]
80[5.0]
4-chlorobenzaldehyde
"
"
1
2
3

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HETEROCYCLES, Vol. 81, No. 10, 2010
NH4OAc
NH3
FePO4
H
R
O
FePO4
NH4OAc
3
O
O
Ph
O
Ph
-H2O
NH3
R
H
HN
Ph
Ph
NH
FePO4
1
6
5
H
OH
H
N
OH
Ph
Ph
N
H
H
R
-H+
Ph
Ph
Ph
Ph
R
-H2O
N
4
H
R
N
H
NH
N
H
9
7
8
Scheme 2. Plausible mechanism for the synthesis of 2,4,5-triarylimidazoles using FePO4
EXPERIMENTAL
Mps were measured by using the capillary tube method with an electro thermal 9200 apparatus. IR
spectra were recorded on Perkin Elmer FT-IR spectrometer did scanning between 4000–400 cm-1. The
1
products were characterized by IR, HNMR. All melting points compared satisfactorily with those
reported in the literature.15, 30, 51, 52
Preparation of 2, 4, 5-triaryl-imidazoles: typical procedure
A mixture of benzaldehyde (1.0 mmol), benzil/benzoin-air exposure (1.0 mmol) and NH4OAc (5.0
mmol), as ammonia source, and FePO4 (10 mol %) stirred refluxing in ethanol (4.0 mL) and air exposure.
The progress of the reaction was monitored by TLC and the spot were detected either UV light or by
placing in iodine chamber. After completion of the reaction, the mixture was filtered, removed catalyst
and the filtrate was cooled to room temperature and the corresponding pure product obtained in 94%
yield.
Spectral and analytical data for new compounds
(E)-4, 5-Diphenyl-2-styryl-1H-imidazole 4d, IR (cm-1, KBr): 3393(N-H), 3027(C-H), 1601(C=C), 1580
(C=N) cm-1. 1H NMR (CDCl3, 500MHz, δppm): 9.38(s, NH), 7.90(d, J=7.45Hz, 1H), 7.26-7.66(m,15 H,
Ph), 7.37(d, J=14.70 Hz, 1H); MS (EI, 70 eV): m/z = 322.147 (100.0%), 323.150 (24.9%), 324.154
(3.0%); Anal. Calcd for C23H18N2: C, 85.68; H, 5.63; N, 8.69. Found: C, 85.21; H, 5.33; N, 8.31.
2-(3,5-Dichlorophenyl)-4,5-diphenyl-1H-imidazole 4f, IR (cm-1, KBr): 3436(N-H), 3060(C-H),
1
1600(C=C), 1591(C=N) cm-1. H NMR(CDCl3, 500MHz, δppm): 10.18(s, NH), 7.17-7.34(m,3H,Ph),
7.37-8.42(m, 10H, Ph); MS (EI, 70 eV): m/z = 364.053 (100.0%), 366.050 (63.9%), 365.057 (22.7%),
367.054 (14.5%), 368.048 (10.2%), 366.060 (2.5%), 369.051 (2.3%), 368.057 (1.6%); Anal. Calcd for

HETEROCYCLES, Vol. 81, No. 10, 2010
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C21H14Cl2N2: C, 69.05; H, 3.86; Cl, 19.41; N, 7.67. Found: C, 68.83; H, 3.59; Cl, 19.06; N, 7.23.
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