Bismuth(III)-SiO2 catalyzed synthesis of polysubstituted imidazoles with the participation of azaaryl derivatives of aniline in four-component reactions

Article abstract of DOI:10.3906/kim-1602-28

A series of novel polyaromatic derivatives of imidazole were synthesized by Bi(III) nitrate-SiO₂ catalyzed four-component reactions of benzil, ammonium acetate, aromatic aldehydes, and N -heterocyclic derivatives of aniline under solvent-free c

Full text of DOI:10.3906/kim-1602-28

Turk J Chem
Turkish Journal of Chemistry
(2016) 40: 729 – 741
¨
http://journals.tubitak.gov.tr/chem/
˙
c
⃝ TUBITAK
doi:10.3906/kim-1602-28
Research Article
Bismuth(III)–SiO2 catalyzed synthesis of polysubstituted imidazoles with the
participation of azaaryl derivatives of aniline in four-component reactions
Zarrin GHASEMI∗, Ziba ZAKERI, Maryam ALLAHVIRDINESBAT
Department of Organic and Biochemistry, Faculty of Chemistry, University of Tabriz, Tabriz, Iran
Received: 08.02.2016
•
Accepted/Published Online: 19.04.2016
•
Final Version: 02.11.2016
Abstract: A series of novel polyaromatic derivatives of imidazole were synthesized by Bi(III) nitrate–SiO2 catalyzed
four-component reactions of benzil, ammonium acetate, aromatic aldehydes, and N -heterocyclic derivatives of aniline
under solvent-free conditions.
Key words: Polysubstituted imidazoles, heterocyclic derivatives of aniline, four-component reactions, Bi(III)-catalyzed
condensations, solvent-free reactions
1. Introduction
Tetrasubstituted imidazole scaffold is an essential part of numerous bioactive compounds,1−6 conjugated and
fluorescent materials,7,8 and metal-coordinating ligands.9,10 Condensation of 1,2-diketones, aryl aldehydes,
primary amines, and ammonium acetate is one of the most common synthetic tools for the preparation of
1,2,4,5-tetrasubstituted imidazoles.11−13 Commercial availability or easy preparation of the individual building
blocks has resulted in the production of highly diverse molecules through this acid-catalyzed reaction.14−17
Continuing efforts and several modifications such as the use of green catalysts and solvent-free conditions indicate
the special interest in this method.18−20 Among the Lewis acids that promote multicomponent reactions, Bi3+
-
based catalysts are popular due to being efficient, inexpensive, and insensitive to air.21−23 In this work, we
report the use of N -heterocyclic derivatives of aniline as a primary amine partner in four-component reactions
in the presence of bismuth nitrate. Because of the multiple applications and interesting properties of the
azole-enriched π-conjugated compounds, especially in terms of electrochemical, optical, and pharmacological
behavior,24−27 and through our interest in the synthesis of polyaromatic heterocyclic frameworks28−30 and also
multicomponent reactions,31 we decided to access such molecules.
2. Results and discussion
We recently reported the tert-BuOK/DMSO-promoted SN Ar reactions of azoles such as imidazole, benzimi-
dazole, pyrazole, and 3-methypyrazole with 4-bromonitrobenzene to obtain N -(4-nitrophenyl) azoles 1a–d.32
Reduction of the nitro group to amine with zinc powder in EtOH/AcOH afforded the required aniline derivatives
2a–d (Scheme).
∗Correspondence: z.ghasemi@tabrizu.ac.ir
729

GHASEMI et al./Turk J Chem
NO2
NH2
X
X
Zn/CH3CO2H, EtOH,
70 oC
Y
N
Y
N
R1
R1
a: X=CH, Y=N, R1=H
b: X=CH, Y=N, R1=H
c: X=N, Y=CH, R1=H
d: X=N, Y=CH, R1=3-Me
1a-d
2a-d
Scheme. Synthesis of heterocyclic derivatives of aniline.
Firstly, we used 4-(3-methyl-1H -pyrazol-1-yl)aniline 2d (1 mmol) in four-component condensation with
benzil (1 mmol), benzaldehyde (1 mmol), and ammonium acetate (1 mmol) to find the optimal reaction
conditions. As shown in Table 1, in the absence of a catalyst, no product was obtained in the presence of solvent
or without solvent, even after 48 h (Entries 1–6). Product formation was observed by using Bi(NO3)3 .5H2 O
Table 1. Optimization of four-component condensation of benzaldehyde, benzyl, ammonium acetate, and aniline 2d
under various conditions.
N
NH2
+
O
H
H3C
N
N
N
H3C
N
N
+
NH4OAc
+
O
O
2d
3a
Lewis acid Catalyst
Entry /mol (%)
a
SiO2 (gr) Conditions
Time
48 h
48 h
48 h
Yield (%)b
-
-
-
Trace
-
-
38
28
30
58
28
35
58
60
78
1
-
-
-
-
-
-
-
-
-
-
-
-
-
-
Solvent-free
H2O
EtOH
Solvent-free
H2O
EtOH
Solvent-free
H2O
EtOH
Solvent-free
H2O
EtOH
R.T
R.T
R.T◦
2
-
3
-
4
-
110 C 48 h
48 h
110 C 48 h
110 C 24 h
110 C 48 h
110 C 48 h
110 C 24 h
110 C 24 h
110 C 24 h
5
-
110◦C
◦
◦
◦
◦
◦
◦
◦
◦
6
-
7
8
9
Bi(NO3)3.5H2O (10)
Bi(NO3)3.5H2O (10)
Bi(NO3)3.5H2O (10)
Bi(NO3)3.5H2O (15)
Bi(NO3)3.5H2O (15)
Bi(NO3)3.5H2O (15)
Bi(NO3)3.5H2O (20)
Bi(NO3)3.5H2O (15) 0.5
Bi(NO3)3.5H2O (15) 0.5
Bi(NO3)3.5H2O (15)
Bi(NO3)3.5H2O (15)
10
11
12
13
14
15
16
17
18
19
20
Solvent-free
Solvent-free
Solvent-free
110 C 24 h
◦
80 C
◦
48 h
110 C 24 h
-
-
ultrasound irradiation-H2O
ultrasound irradiation-EtOH 70 Hzc 30 min Trace
ultrasound irradiation-H2O
70 Hzc 30 min 20
ultrasound irradiation-EtOH 70 Hzc 30 min 23
MW irradiation 200-W 30 min 25
70 Hzc 30 min Trace
Bi(NO3)3.5H2O (15) 0.5
Bi(NO3)3.5H2O (15) 0.5
Bi(NO3)3.5H2O (15) 0.5
aReaction progress monitored by TLC. Isolated yield. cFrequency of sonication
b
730

GHASEMI et al./Turk J Chem
(10 mol%) but with low yields (Entries 7–9). Relatively high efficiency was achieved with a larger amount of
catalyst (15 mol%) in solvent-free conditions (Entry 10). By increasing the catalyst loading to 20 mol%, there
was no considerable change in the yield of the reaction (Entry 13). To access better reactivity, we then mixed
the bismuth catalyst with silica (0.5 g), which led to a more favorable outcome (Entry 14). Application of silica
as cocatalyst has been reported in some metal-promoted reactions.33−36 Conventional heating of reactants with
the mixed catalytic system at 110 ◦ C for 24 h, resulted in the product 3a in 78% yield (Entry 15). We also
evaluated the effect of ultrasonic irradiation on the progress of this reaction. Sonication of the reactants at 70
Hz with different reaction media did not lead to a significant product (Entries 16–19).
Microwave irradiation under 200 W had no accelerator effect even when the microwave power was
increased (Entry 20). We then synthesized various other derivatives of this type with amines 2a–d under
the optimized conditions (Table 1, entry 15). Table 2 shows the yields and melting points of the corresponding
products 3a–k, which were produced in the presence of amines 2d or 4-(1H -pyrazol-1-yl)aniline 2c. Treatment
of 2d with 2-thiophene carbaldehyde, benzil, and ammonium acetate also gave the product 3l in 70% yield
(Figure 1).
Table 2. Bismuth (III)-nitrate-SiO2 catalyzed synthesis of highly substituted imidazoles (3a–k) with the participation
of 4-(pyrazol-1-yl)anilines (2c,d).
R
NH2
+
N
O
H
R1
N
N
N
R1
N
N
+
NH4OAc
+
Bi(NO3)3 / SiO2
O
O
2c,d
R
3a-k
Entry R1
1
R
H
Product Yield (%) mp (◦C)
CH3
3a
3b
78
70
69
70
67
63
56
71
65
62
65
244–246
212–214
218–219
224–226
238–240
228–229
240–242
250–252
242–244
216–218
236–238
2
CH3 4-CH3
3
CH3 4-CH(CH3)2 3c
4
5
6
CH3 4-OMe
CH3 4-Cl
CH3 3-Br
3d
3e
3f
3g
3h
3i
7
CH3 4-N(CH3)2
8
9
10
11
H
H
H
H
H
4-CH3
4-CH(CH3)2 3j
4-OMe 3k
The scope of these reactions was explored using 4-(1H -imidazol-1-yl)aniline 2a (Table 3) and 4-(1H -
benzimidazol-1-yl)aniline 2b (Table 4) to afford the products 4a–f and 5a–f, respectively. The C-2 carbon
peak values of compounds 5a–f in their 13 C NMR spectra were found to be similar to values reported in
the literature.37,38 The imidazole 4g was also obtained with the participation of amine 2a and 2-thiophene
carbaldehyde in 71% yield (Figure 1). Therefore, a variety of polyaromatic derivatives of imidazoles were
obtained under simple workup and in good yields.
731

GHASEMI et al./Turk J Chem
S
S
N
N
N
N
H3C
N
N
N
N
3l (70%)
4g (71%)
Figure 1. Highly substituted imidazoles possessing thiophene ring.
Table 3. Bismuth(III) nitrate-SiO2 catalyzed synthesis of highly substituted imidazoles (4a–f) with the participation
of 4-(imidazol-1-yl)aniline 2a.
R
NH2
N
N
O
H
N
N
N
N
+
+
NH4OAc
+
Bi(NO3)3 / SiO2
O
O
2a
R
4a-f
Entry
R
H
CH3
Product Yield (%) mp (◦C)
1
2
3
4
5
6
4a
4b
70
71
73
68
72
56
250–252
262–264
266–268
248–250
258–260
330–332
CH(CH3)2 4c
Cl
OMe
OH
4d
4e
4f
Regarding the above reactions, it should be mentioned that, in the presence of 4-nitrobenzaldehyde,
2,4,5-triarylimidazoles were produced through three-component cyclizations without the involvement of the
substituted aniline.
A probable mechanism for the catalytic participation of Bi(NO3)3 .5H2 O-SiO2 in the synthesis of target
molecules is postulated in Figure 2. Because silica alone was not able to catalyze this reaction, it seems SiO2 -
coordinated Bi3+ activates the carbonyl group of an aldehyde to simplify the formation of diamine intermediate
A. Bi(NO3)3 .5H2 O-SiO2 also activates the benzil to promote condensation with A to give the species B.
Elimination of water from B transformed it into the desired imidazole derivatives (Figure 2).
3. Experimental
Melting points were determined on an Electrothermal MEL-TEMP apparatus (model 1202D) and are uncor-
rected. FT-IR spectra were obtained with a Bruker Tensor 27 spectrometer; ν in cm−1
.
1 H and 13 C NMR
spectra were recorded with a Bruker Spectrospin Avance 400 spectrometer operating at 400 MHz and 100
MHz, respectively, in DMSO-d6 ; chemical shifts are given in parts per million (ppm, δ) relative to residual
solvent peaks as standard at 298 K (2.50 ppm (1 H), 39.5 ppm (13 C)); J in Hz. Elemental analyses were
measured by Vario EL III apparatus (Elementar Co.). The microwave experiment was conducted in a Milestone
MicroSYNTH apparatus. Ultrasonic mediated experiments were carried out by use of an ultrasonic processor
732

GHASEMI et al./Turk J Chem
Table 4. Bismuth(III) nitrate-SiO2 catalyzed synthesis of highly substituted imidazoles (5a–f) with the participation
of 4-(benzimidazol-1-yl)aniline 2b.
R
NH2
+
N
N
O
H
N
N
N
+
NH4OAc
+
N
Bi(NO3)3 / SiO2
O
O
2b
R
5a-f
Entry
R
H
4-CH3
Product Yield (%) mp (◦C)
1
2
3
4
5
6
5a
5b
68
63
70
67
73
70
260–262
242–244
240–242
274–276
242–244
240–242
4-CH(CH3)2 5c
4-Cl
4-OMe
3-Br
5d
5e
5f
X=CH, Y=N, R1=H
X=CH, Y=N, R1=H
X=N, Y=CH, R1=H
X=N, Y=CH, R1=3-Me
NH2
X
Y
N
R1
H
Ar
NH
1a-d
NH4OAc
X
Y
R1
Ar
N
H
H2O
N
N
H
OH
Ar
O
O
B
A
Bi(NO3)3.5H2O
Y
N
H
OH
Si
O
O
OH
Si
X
R1
Y
X
R1
H2N
Ar
Ar
N
Si
Si
N
N
H
O
O
O
O
HN
O
O
Bi(NO3)3.5H2O
2-4
Bi(NO3)3.5H2O
H2O
Ar
O
OH
O
O
OH
Si
OH
Si
O
O
OH
Si
Si
O
Si
Si
Si
Si
H
O
O
O
O
O
O
O
O
O
Figure 2. Probable mechanism for the four-component reactions with the participation of azaaryl derivatives of aniline
in the presence of Bi(NO3)3 .5H2 O-SiO2 .
probe (SONOPULS Ultrasonic homogenizers). The used silica gel cocatalyst was Kieselgel 60 (0.040–0.063 mm,
Merck: 9385).
3.1. Synthesis of substituted imidazoles (3–5)
A mixture of N -(4-aminophenyl) azoles 2a–d (1 mmol), benzil (1 mmol, 0.21 g), aromatic aldehyde (1 mmol),
and ammonium acetate (1 mmol, 0.077 g) was stirred vigorously. Bi(NO3)3 .5H2 O (0.15 mmol, 0.073 g, 15
mol%) and SiO2 (0.5 g) were mixed effectively and added to the mixed reactants. The resulting mixture was
heated at 110 ◦ C for 24 h. Acetone (50 mL) was then added and the mixture was stirred at 50 ◦ C for 10 min.
733

GHASEMI et al./Turk J Chem
Filtering the hot mixture and then concentration of the filtrate produced the crude product. Recrystallization
of the crude products in 96% EtOH gave the desired product 3–5.
3.1.1. 1-[4-(3-Methyl-1H -pyrazol-1-yl)phenyl]-2,4,5-triphenyl-1H -imidazole (3a)
Pale yellow solid; Yield 0.35 g (78%) mp 244–246 ◦ C. FTIR (KBr): ν¯ 3054, 2925, 1517, 1475, 846, 693 cm−1
;
1 H NMR (DMSO-d6): 2.23 (s, 3H, CH3), 6.32 (d, J = 2.4 Hz, 1H, py-H4), 7.17–7.35 (m, 13H, Ar-H), 7.43–7.44
(m, 2H, Ar-H), 7.50 (d, J = 7.9 Hz, 2H, Ar-H), 7.72 (d, J = 8.8 Hz, 2H, Ar-H), 8.37 (d, J = 2.4 Hz, 1H,
py-H5). 13 C NMR (DMSO-d6): δ = 13.4, 108.3 (Py-C4), 117.9, 126.4, 126.5, 128.1, 128.2, 128.3, 128.4, 128.5,
128.52, 129.8, 130.3, 130.34, 131.1, 131.3, 133.7, 134.3, 136.8, 139.2, 146.1 (Im-C2), 150.2 (Py-C3). Anal. Calcd.
For C31 H24 N4 : C, 82.27; H, 5.35; N, 12.38; Found: C, 81.98; H, 5.12; N, 12.55%.
3.1.2. 4,5-Diphenyl-1-[4-(3-methyl-1H -pyrazol-1-yl)phenyl]-2-(p-tolyl)-1H -imidazole (3b)
Yield: 0.32 g (70%); pale yellow solid; mp 212–214 ◦ C; FTIR (KBr): ν¯ 3049, 2924, 1522, 1362, 1035 cm−1
;
1 H NMR (400 MHz, DMSO-d6): δ 2.23 (s, 3H, CH3), 2.26 (s, 3H, CH3), 6.33 (s, 1H, Py-H4), 7.11–7.34 (m,
14H, Ar-H), 7.48 (d, J = 7.5 Hz, 2H, Ar-H), 7.71 (d, J = 8.6 Hz, 2H, Ar-H), 8.37 (s, 1H, py-H5). 13 C NMR
(100 MHz, DMSO-d6): δ 13.4, 20.8, 108.3 (Py-C4), 117.2, 126.3, 126.5, 127.5, 128.2, 128.3, 128.4, 128.6, 128.8,
129.9, 130.4, 131.2, 133.8, 134.4, 136.7, 137.9, 139.2, 150.2 (Py-C3). Anal. Calcd. For C32 H26 N4 : C 82.38, H
5.62, N 12.01; Found, C 82.15, H 5.39, N 12.34.
3.1.3. 2-(4-Isopropylphenyl)-1-[4-(3-methyl-1H -pyrazol-1-yl)phenyl]-4,5-Diphenyl-1H -imidazole
(3c)
Yield: 0.34 g (69%); pale yellow solid; mp 218–219 ◦ C; FTIR (KBr): ν¯ 3046, 2957, 1522, 1361, 840, 654 cm−1
;
1 H NMR (400 MHz, DMSO-d6): δ 1.15 (d, J = 6.9 Hz, 6H, (CH3)2 CH), 2.23 (s, 3H, CH3), 2.82 (m, 1H,
CH (Me)2), 6.33 (d, J = 2.2 Hz, 1H, Py-H4), 7.17–7.37 (m, 14H, Ar-H), 7.49 (d, J = 7.3 Hz, 2H, Ar-H),
7.73 (d, J = 8.7 Hz, 2H, Ar-H), 8.37 (d, J = 2.3 Hz, 1H, Py-H5). 13 C NMR (100 MHz, DMSO-d6): δ 13.4,
23.6, 33.1, 108.3 (Py-C4), 117.9, 126.2, 126.3, 126.4, 127.9, 128.1, 128.2, 128.4, 128.5, 129.9, 130.4, 131.1, 131.2,
133.8, 134.4, 136.7, 139.2, 146.1 (Im-C2), 148.6 (=C-i Pr), 150.2 (Py-C3). Anal. Calcd. For C34 H30 N4 : C
82.56, H 6.11, N 11.33; Found, C 82.29, H 6.34, N 11.65.
3.1.4. 2-(4-methoxyphenyl)-1-[4-(3-methyl-1H -pyrazol-1-yl) phenyl]-4,5-diphenyl-1H -imidazole
(3d)
Yield: 0.328 g (70%); pale yellow solid; mp 224–226 ◦ C; FTIR (KBr): ν¯ 3048, 2929, 1607, 1523, 1248, 944
cm−1
.
1 H NMR (400 MHz, DMSO-d6): δ = 2.23 (s, 3H, CH3), 3.72 (s, 3H, OCH3), 6.33 (s, 1H, Py-H4),
6.87 (d, J = 8.5 Hz, 2H, Ar-H), 7.15–7.37 (m, 12H, Ar-H), 7.49 (d, J = 7.9 Hz, 2H, Ar-H), 7.72 (d, J = 8.5
Hz, 2H, Ar-H), 8.37 (s, 1H, Py-H5). 13 C NMR (100 MHz, DMSO-d6): δ = 13.4, 55.1 (OCH3), 108.3 (Py-C4),
113.7, 117.9, 122.7, 126.3, 126.4, 128.2, 128.4, 128.5, 129.7, 129.9, 130.5, 130.9, 131.2, 133.9, 134.5, 136.6, 139.2,
146.1 (Im-C2), 150.2 (Py-C3), 159.3 (=C-OMe). Anal. Calcd. For C32 H26 N4 O: C 79.64, H 5.43, N 11.61;
Found, C 79.32, H 5.19, N 11.87.
734

GHASEMI et al./Turk J Chem
3.1.5. 2-(4-Chlorophenyl)-1-[4-(3-methyl-1H -pyrazol-1-yl) phenyl]-4,5-diphenyl-1H -imidazole (3e)
Yield: 0.32 g (67%); pale yellow solid; mp 238–240 ◦ C; FTIR (KBr): ν¯ 3051, 2957, 1611, 1516, 1312, 840
cm−1
.
1 H NMR (400 MHz, DMSO-d6): δ = 2.24 (s, 3H, CH3), 6.33 (d, J = 2.2 Hz, 1H, Py-H4), 7.18–7.51
(m, 16H, Ar-H), 7.74 (d, J = 8.7 Hz, 2H, Ar-H), 8.38 (d, J = 2.2 Hz, 1H, Py-H5). 13 C NMR (100 MHz,
DMSO-d6): δ = 13.4, 108.3 (Py-C4), 118.0, 126.3, 126.6, 128.2, 128.4, 128.6, 129.1, 129.8, 129.9, 130.2, 131.1,
131.6, 133.2, 133.5, 134.2, 137.0, 139.3, 144.9, 150.3 (Py-C3). Anal. Calcd. For C31 H23 ClN4 : C 76.46, H 4.76,
N 11.50; Found, C 76.19, H 4.91, N 11.80.
3.1.6. 2-(3-Bromophenyl)-1-[4-(3-methyl-1H -pyrazol-1-yl) phenyl]-4,5-diphenyl-1H -imidazole (3f)
Yield: 0.33 g (63%); pale yellow solid; mp 228–229 ◦ C; FTIR (KBr): ν¯ 3057, 2929, 1598, 1519, 1362, 691
cm−1
.
1 H NMR (400 MHz, DMSO-d6): δ = 2.24 (s, 3H, CH3), 6.34 (d, J = 2.1 Hz, 1H, Py-H4), 7.17–7.33
(m, 11H, Ar-H), 7.39 (d, J = 8.7 Hz, 2H, Ar-H), 7.50 (d, J = 7.1 Hz, 2H, Ar-H), 7.69 (s, 1H, Ar-H), 7.75 (d,
J = 8.7 Hz, 2H, Ar-H), 8.39 (d, J = 2.1 Hz, 1H, Py-H5). 13 C NMR (100 MHz, DMSO-d6): δ = 13.5, 108.4
(Py-C4), 117.9, 121.5, 126.4, 126.7, 126.9, 128.3, 128.6, 129.9, 130.1, 130.4, 130.8, 131.1, 131.9, 132.4, 133.4,
134.1, 137.1, 139.4, 144.4, 150.3 (Py-C3). Anal. Calcd. For C31 H23 BrN4 : C 70.06, H 4.36, N 10.54; Found, C
69.79, H 4.53, N 10.28.
3.1.7. 2-[4-(N ,N -Dimethylamino)phenyl]-1-[4-(3-methyl-1H -pyrazol-1-yl) phenyl]-4,5-diphenyl-
1H -imidazole (3g)
Yield: 0.28 g (56%); pale yellow solid; mp 240–242 ◦ C; FTIR (KBr): ν¯ 3057, 2925, 1605, 1522, 1359, 825
cm−1 1 H NMR (400 MHz, DMSO-d6): δ 2.24 (s, 3H, CH3), 2.87 (s, 6H, N-CH3), 6.33 (d, J = 1.9 Hz,
;
1H, Py-H4), 6.60 (d, J = 8.8 Hz, 2H, Ar-H), 7.14–7.39 (m, 12H, Ar-H), 7.48 (d, J = 7.8 Hz, 2H, Ar-H), 7.72
(d, J = 8.6 Hz, 2H, Ar-H), 8.37 (d, J = 1.9 Hz, 1H, Py-H5). 13 C NMR (100 MHz, DMSO-d6): δ 13.4,
55.1 (N(CH3)2), 108.3 (Py-C4), 111.4, 11.9, 117.4, 117.9, 126.3, 126.7, 127.9, 128.1, 128.3, 128.5, 129.1, 129.9,
130.5, 130.6, 131.2, 134.2, 134.5, 139.1, 146.8 (Im-C2), 150.0 (Py-C3), 150.2 (=C–NMe2). Anal. Calcd. For
C33 H29 N5 : C 79.97, H 5.90, N 14.13; Found, C 79.69, H 6.18, N 14.51.
3.1.8. 1-[4-(1H -pyrazol-1-yl)phenyl]-2,4,5-triphenyl-1H -imidazole (3h)
Yield: 0.31 g (71%); pale yellow solid; mp 250–252 ◦ C; FTIR (KBr): ν¯ 3054, 1517, 1391, 846, 693 cm−1
;
1 H NMR (400 MHz, DMSO-d6): δ 6.33 (d, J = 2.4 Hz, 1H, Py-H4), 7.18–7.36 (m, 14H, Ar-H), 7.43–7.44
(m, 2H, Ar-H), 7.50 (d, J = 7.9 Hz, 2H, Ar-H), 7.72 (d, J = 8.8 Hz, 2H, Ar-H), 8.37 (d, J = 2.4 Hz, 1H,
Py-H5). 13 C NMR (100 MHz, DMSO-d6): δ 108.3 (Py-C4), 117.9, 126.3, 126.5, 128.1, 128.2, 128.3, 128.4,
128.5, 129.9, 130.3, 130.34, 131.1, 131.3, 133.7, 134.3, 136.8, 139.2, 146.1 (Im-C2), 150.2 (Py-C3). Anal. Calcd.
For C30 H22 N4 : C 82.17, H 5.06, N 12.78; Found, C 81.85, H 5.24, N 12.56.
3.1.9. 4,5-Diphenyl-1-[4-(1H -pyrazol-1-yl)phenyl]-2-(p-tolyl)-1H -imidazole (3i)
Yield: 0.29 g (65%); pale yellow solid; mp 242–244 ◦ C; FTIR (KBr): ν¯ 3065, 2923, 1520, 1364, 839, 696 cm−1
;
1 H NMR (400 MHz, DMSO-d6): δ 2.26 (s, 3H, CH3), 6.33 (d, J = 2.1 Hz, 1H, Py-H4), 7.11 (d, J = 7.9 Hz,
2H, Ar-H), 7.15–7.38 (m, 13H, Ar-H), 7.49 (d, J = 7.5 Hz, 2H, Ar-H), 7.71 (d, J = 8.6 Hz, 2H, Ar-H), 8.36
735

GHASEMI et al./Turk J Chem
(d, J = 2.1 Hz, 1H, Py-H5). 13 C NMR (100 MHz, DMSO-d6): δ 20.7, 108.2 (Py-C4), 117.9, 118.4, 126.3,
126.4, 127.5, 127.9, 128.1, 128.2, 128.4, 128.5, 128.8, 128.9, 130.0, 130.4, 131.1, 133.8, 134.4, 137.9, 139.2, 146.2
(Im-C2), 150.2 (Py-C3). Anal. Calcd. For C31 H24 N4 : C 82.27, H 5.35, N 12.38; Found, C 81.95, H 5.17, N
12.64.
3.1.10. 4,5-Diphenyl-2-(4-isopropylphenyl)-1-[4-(1H -pyrazol-1-yl)]phenyl]-1H -imidazole (3j)
Yield: 0.30 g (62%); pale yellow solid; mp 216–218 ◦ C; FTIR (KBr): ν¯ 3047, 2956, 1616, 1530, 1362, 840 cm−1
;
1 H NMR (400 MHz, DMSO-d6): δ 1.15 (d, J = 6.9 Hz, 6H, (CH3)2 CH), 2.82–2.84 (m, 1H, CH (Me)2), 6.33
(d, J =1 Hz, 1H, Py-H4), 7.16–7.41 (m, 15H, Ar-H), 7.50 (d, J = 7.8 Hz, 2H, Ar-H), 7.73 (d, J = 8.5 Hz,
2H, Ar-H), 8.37 (d, J = 1 Hz, 1H, Py-H5). 13 C NMR (100 MHz, DMSO-d6): δ 23.6, 33.1, 108.2 (Py-C4),
117.9, 118.4, 126.1, 126.3, 126.4, 127.9, 128.1, 128.2, 128.4, 128.5, 129.9, 130.0, 130.4, 131.1, 133.8, 134.4, 136.7,
139.2, 146.1 (Im-C2), 148.6 (=C-i Pr), 150.2 (Py-C3). Anal. Calcd. For C33 H28 N4 : C 82.47, H 5.87, N 11.66;
Found, C 82.16, H 5.65, N 11.89.
3.1.11. 4,5-Diphenyl-2-(4-methoxyphenyl)-1-[4-(1H -pyrazol-1-yl)]phenyl]-1H -imidazole (3k)
Yield: 0.30 g (65%); pale yellow solid; mp 236–238 ◦ C; FTIR (KBr): ν¯ 3054, 2924, 1602, 1524, 1251, 843
cm−1 1 H NMR (400 MHz, DMSO-d6): δ 3.72 (s, 3H, OCH3), 6.33 (d, J = 2.2 Hz, 1H, Py-H4), 6.87 (d, J =
;
8.7 Hz, 2H, Ar-H), 7.15–7.37 (m, 13H, Ar-H), 7.49 (d, J = 7.4 Hz, 2H, Ar-H), 7.72 (d, J = 8.7 Hz, 2H, Ar-H),
8.37 (d, J = 2.2 Hz, 1H, Py-H5). 13 C NMR (100 MHz, DMSO-d6): δ 55.1 (OCH3), 108.3 (Py-C4), 113.7,
117.9, 122.7, 126.3, 126.4, 128.1, 128.4, 128.5, 129.7, 129.9, 130.5, 130.9, 131.2, 133.9, 134.5, 136.6, 139.2, 146.1
(Im-C2), 150.2 (Py-C3), 159.3 (=C–OMe). Anal. Calcd. For C31 H24 N4 O: C 79.46, H 5.16, N 11.96; Found,
C 79.17, H 5.38, N 11.73.
3.1.12. 4,5-Diphenyl-1-[4-(3-methyl-1H -pyrazol-1-yl)phenyl]- 2-(thiophen-2-yl)-1H -imidazole (3l)
Yield: 0.32 g (70%); pale yellow solid; mp 244–246 ◦ C; FTIR (KBr): ν¯ 3056, 2926, 1615, 1515, 1359, 695
cm−1 1 H NMR (400 MHz, DMSO-d6): δ 2.25 (s, 3H, CH3), 6.35 (d, J = 2.1 Hz, 1H, Py-H4), 6.62 (d, J
;
= 3.6 Hz, 1H, Th-H5), 6.93–7.95 (m, 1H, Th-H4), 7.18–7.30 (m, 8H, Ar-H), 7.47–7.53 (m, 5H, Ar-H), 7.83 (d,
J = 8.7 Hz, 2H, Ar-H), 8.43 (d, J = 2.1 Hz, 1H, Py-H5). 13 C NMR (100 MHz, DMSO-d6): δ 13.5, 108.4
(Py-C4), 118.2, 125.6, 126.3, 126.6, 127.2, 127.6, 128.2, 128.5, 128.6, 130.0, 130.4, 131.1, 131.4, 132.8, 133.1,
134.0, 136.8, 140.0, 141.5 (Th-C2), 150.4 (Py-C3). Anal. Calcd. For C29 H22 N4 S: C 75.95, H 4.84, N 12.22, S
6.99; Found, C 75.62, H 4.65, N 11.98, S 6.72.
3.1.13. 1-(4-(1H -imidazol-1-yl)phenyl)-2,4,5-triphenyl-1H -imidazole (4a)
Yield: 0.31 g (70%); pale yellow solid; mp 250–252 ◦ C; FTIR (KBr): ν¯ 3056, 1524, 1443, 847, 696 cm−1 1 H
;
NMR (400 MHz, DMSO-d6): δ 7.15–7.32 (m, 12H, Ar-H), 7.42–7.51 (m, 6H, Ar-H), 7.68 (d, J = 8.7 Hz, 2H,
Ar-H), 7.84 (s, 1H, Im-H4), 8.39 (s, 1H, Im-H2). 13 C NMR (100 MHz, DMSO-d6): δ 120.3, 125.2, 126.3, 126.5,
127.1, 128.0, 128.2, 128.3, 128.4, 128.6, 128.7, 129.5, 129.9, 130.2, 130.3, 131.2, 131.3, 134.3, 135.1, 136.3, 136.9,
146.21 (N=CAr-N). Anal. Calcd. For C30 H22 N4 : C 82.17, H 5.06, N 12.78; Found, C 81.88, H 5.29, N 12.56.
736

GHASEMI et al./Turk J Chem
3.1.14. 4,5-Diphenyl-1-[4-(1H -imidazol-1-yl)phenyl]-2-(p-tolyl)-1H -imidazole (4b)
Yield: 0.32 g (71%); pale yellow solid; mp 262–264 ◦ C; FTIR (KBr): ν¯ 3058, 2919, 1605, 1525, 1376, 698
cm−1 1 H NMR (400 MHz, DMSO-d6): δ 2.26 (s, 3H, CH3), 7.11–7.33 (m, 13H, Ar-H), 7.42 (d, J = 8.7
;
Hz, 2H, Ar-H), 7.48 (d, J = 7.4 Hz, 2H, Ar-H), 7.66 (d, J = 8.7 Hz, 2H, Ar-H), 7.82 (s, 1H, Im-H5), 8.36 (s,
1H, Im-H2). 13 C NMR (100 MHz, DMSO-d6): δ = 20.8, 117.8, 120.2, 126.4, 126.5, 127.5, 128.2, 128.4, 128.6,
128.9, 129.6, 130.0, 130.4, 131.1, 131.2, 134.4, 135.1, 135.7, 136.4, 136.8, 138.0, 146.4 (N=CAr-N). Anal. Calcd.
For C31 H24 N4 : C 82.27, H 5.35, N 12.38; Found, C 81.98, H 5.54, N 12.65.
3.1.15. 4,5-Diphenyl-1-[4-(1H -imidazol-1-yl)phenyl]-2-(4-isopropylphenyl)-1H -imidazole (4c)
Yield: 0.35 g (73%); pale yellow solid; mp 266–268 ◦ C; FTIR (KBr): ν¯ 3065, 2961, 1524, 1419, 1151 cm−1 1 H
;
NMR (400 MHz, DMSO-d6): δ 1.16 (d, J = 6.9 Hz, 6H, (CH3)2 CH), 2.82–2.85 (m, 1H, (Me)2 CH), 7.15–7.36
(m, 13H, Ar-H), 7.46–7.49 (m, 4H, Ar-H), 7.70 (d, J = 8.7 Hz, 2H, Ar-H), 7.87 (s, 1H, Im-H5), 8.41 (s, 1H,
Im-H2). 13 C NMR (100 MHz, DMSO-d6): δ 23.6, 33.1, 117.9, 120.3, 126.3, 126.4, 126.5, 127.9, 128.2, 128.3,
128.6, 129.8, 130.4, 130.5, 131.2, 131.24, 134.4, 135.3, 135.8, 136.3, 136.8, 146.3 (N=CAr-N), 148.7 (=C-Pri).
Anal. Calcd. For C33 H28 N4 : C 82.47, H 5.87, N 11.66; Found, C 82.19, H 5.63, N 11.87.
3.1.16. 2-(4-Chlorophenyl)-4,5-diphenyl-1-[4-(1H -imidazol-1-yl)phenyl]-1H -imidazole (4d)
Yield: 0.32 g (68%); pale yellow solid; mp 248–250 ◦ C; FTIR (KBr): ν¯ 3065, 1524, 1396, 842, 699 cm−1 1 H
;
NMR (400 MHz, DMSO-d6): δ 7.11 (s, 1H, Im-H4), 7.18–7.50 (m, 16H, Ar-H), 7.68 (d, J = 8.7 Hz, 2H, Ar-H),
7.82 (s, 1H, Im-H5), 8.36 (s, 1H, Im-H2). 13 C NMR (100 MHz, DMSO-d6): δ 117.7, 120.2, 126.3, 126.6, 128.2,
128.4, 128.5, 128.6, 129.1, 129.9, 130.1, 130.2, 131.1, 131.3, 131.5, 133.2, 134.1, 134.6, 135.6, 136.6, 137.1, 145.0
(N=CAr–N). Anal. Calcd. For C30 H21 ClN4 : C 76.18, H 4.48, N 11.85; Found, C 76.47, H 4.26, N 11.59.
3.1.17. 4,5-Diphenyl-1-[4-(1H -imidazol-1-yl)phenyl]-2-(4-methoxyphenyl)-1H -imidazole (4e)
Yield: 0.34 g (72%); pale yellow solid; mp 258–260 ◦ C; FTIR (KBr): ν¯ 3057, 2925, 1527, 1384, 843, 698
cm−1 1 H NMR (400 MHz, DMSO-d6): δ 3.72 (s, 3H, OCH3), 6.88 (d,J = 8.8 Hz, 2H, Ar-H), 7.15–7.50
;
(m, 15H, Ar-H), 7.70 (d, J = 8.7 Hz, 2H, Ar-H), 7.89 (s, 1H, Im-H5), 8.47 (s, 1H, Im-H2). 13 C NMR (100
MHz, DMSO-d6): δ 55.1 (OCH3), 113.7, 120.5, 122.7, 126.3, 126.4, 128.0, 128.2, 128.5, 128.6, 129.5, 129.6,
129.8, 130.4, 130.8, 131.2, 134.4, 135.5, 136.1, 136.7, 146.2 (N=CAr–N), 159.3 (=C–OMe). Anal. Calcd. For
C31 H24 N4 O: C 79.46, H 5.16, N 11.96; Found, C 79.19, H 5.28, N 11.73.
3.1.18. 4-{4,5-Diphenyl-1-[4-(1H -imidazol-1-yl)phenyl]-1H -imidazol-2-yl} phenol (4f)
Yield: 0.25 g (56%); pale yellow solid; mp 330–332 ◦ C; FTIR (KBr): ν¯ 3414, 1520, 1478, 840, 699 cm−1
;
1 H NMR (400 MHz, DMSO-d6): δ 6.68–6.70 (m, 2H, Ar-H), 7.09 (s, 1H, Im-H4), 7.14–7.18 (m, 1H, Ar-H),
7.24–7.32 (m, 9H, Ar-H), 7.36–7.40 (m, 2H, Ar-H), 7.48 (d, J = 7.9 Hz, 2H, Ar-H), 7.63–7.66 (m, 2H, Ar-H),
7.78 (s, 1H, Im-H5), 8.32 (s, 1H, Im-H2), 9.70 (s, 1H, OH). 13 C NMR (100 MHz, DMSO-d6): δ 114.9, 115.0,
117.6, 120.0, 126.3, 128.1, 128.4, 128.5, 129.9, 130.1, 130.3, 130.5, 130.6, 131.2, 134.5, 135.0, 135.4, 136.3, 136.5,
146.6 (N=CAr–N), 157.5, 157.6 (=C-OH). Anal. Calcd. For C30 H22 N4 O: C 79.27, H 4.88, N 12.33; Found, C
78.94, H 4.62, N 12.54.
737

GHASEMI et al./Turk J Chem
3.1.19. 4,5-Diphenyl-1-[4-(1H -imidazol-1-yl)phenyl]-2-(thiophen-2-yl)-1H -imidazole (4g)
Yield: 0.31 g (71%); pale yellow solid; mp 256–258 ◦ C; FTIR (KBr): ν¯ 3065, 1517, 1296, 702 cm−1 1 H NMR
;
(400 MHz, DMSO-d6): δ = 6.61 (d, J = 3.2 Hz, 1H, Im-H4), 6.93–6.96 (m, 1H, Th-H4), 7.12–7.22 (m, 9H,
Ar-H), 7.47 (d, J = 7.4 Hz, 2H, Ar-H), 7.52 (d, J = 4.8 Hz, 1H, Th-H5), 7.61 (d, J = 8.6 Hz, 2H, Ar-H),
7.76 (d, J = 8.6 Hz, 2H, Ar-H), 7.85 (s, 1H, Im-H5), 8.38 (s, 1H, Im-H2). 13 C NMR (100 MHz, DMSO-d6): δ
117.7, 120.4, 125.7, 126.3, 126.6, 127.3, 127.6, 128.2, 128.6, 128.7, 129.9, 130.2, 130.8, 131.1, 131.3, 132.7, 134.0,
134.3, 135.6, 136.9, 137.2, 141.5 (Th-C2). Anal. Calcd. For C28 H20 N4 S: C 75.65, H 4.53, N 12.60, S 7.21;
Found, C 75.92, H 4.68, N 12.44, S 7.56.
3.1.20. 1-[4-(2,4,5-Triphenyl-1H -imidazol-1-yl)phenyl]-1H -benzo[d]imidazole (5a)
Yield: 0.32 g (68%); pale yellow solid; mp 260–262 ◦ C; FTIR (KBr): ν¯ 3050, 1514, 1228, 693 cm−1 1 H NMR
;
(400 MHz, DMSO-d6): δ 7.19–7.20 (m, 1H, Benzim-H5), 7.25–7.37 (m, 11H, Ar-H), 7.46–7.56 (m, 8H, Ar-H),
7.66–7.69 (m, 2H, Ar-H), 7.75–7.77 (m, 1H, Ar-H), 8.59 (s, 1H, Benzim-H2). 13 C NMR (100 MHz, DMSO-d6):
δ 110.6, 120.1, 122.7, 123.7, 123.9, 126.4, 126.6, 128.2, 128.3, 128.4, 128.5, 128.6, 130.2, 130.3, 130.5, 131.2,
131.3, 132.7, 134.3, 135.6, 135.9, 136.9, 143.2, 143.8 (Benzim-C2), 146.3 (Im-C2). Anal. Calcd. For C34 H24 N4 :
C 83.58, H 4.95, N 11.47; Found, C 83.87, H 4.69, N 11.26.
3.1.21. 1-{4-[4,5-Diphenyl-2-(p-tolyl)-1H -imidazol-1-yl]phenyl} -1H -benzo[d] imidazole (5b)
Yield: 0.32 g (63%); pale yellow solid; mp 242–244 ◦ C; FTIR (KBr): ν¯ 3056, 2923, 1517, 1455, 1023, 696
cm−1 1 H NMR (400 MHz, DMSO-d6): δ 2.27 (s, 3H, CH3), 7.14 (d, J = 8.0 Hz, 2H, Ar-H), 7.19 (d, J
;
= 7.1 Hz, 1H, Benzim-H7), 7.24–7.27 (m, 2H, Ar-H), 7.31–7.36 (m, 9H, Ar-H), 7.50–7.54 (m, 5H, Ar-H), 7.67
(d, J = 8.5 Hz, 2H, Ar-H), 7.77 (d, J = 7.6 Hz, 1H, Benzim-H4), 8.58 (s, 1H, Benzim-H2). 13 C NMR (100
MHz, DMSO-d6): δ 20.8, 110.6, 120.1, 122.7, 123.7, 123.9, 126.4, 126.5, 127.5, 128.2, 128.4, 128.5, 128.6, 128.9,
130.3, 130.5, 131.1, 131.2, 132.7, 134.4, 135.7, 135.9, 136.9, 138.0, 143.2, 143.8 (Benzim-C2), 146.4 (Im-C2).
Anal. Calcd. For C35 H26 N4 : C 83.64, H 5.21, N 11.15; Found, C 83.95, H 5.09, N 11.37.
3.1.22. 1-{4-[4,5-Diphenyl-2-(4-isopropylphenyl)-1H -imidazol-1-yl]phenyl} -1H -benzo[d]imidazole
(5c)
Yield: 0.37 g (70%); pale yellow solid; mp 240–242 ◦ C; FTIR (KBr): ν¯ 3055, 2958, 1515, 1453, 841, 698 cm−1
;
1 H NMR (400 MHz, DMSO-d6): δ 1.16 (d, J = 6.9 Hz, 6H, (CH3)2 CH), 2.82–2.89 (m, 1H, CH (Me)2),
7.16–7.29 (m, 5H, Ar-H), 7.30–7.37 (m, 7H, Ar-H), 7.39 (d, J = 8.2 Hz, 2H, Ar-H), 7.50–7.52 (m, 3H, Ar-H),
7.55 (d, J = 8.6 Hz, 2H, Ar-H), 7.69 (d, J = 8.6 Hz, 2H, Ar-H), 7.76–7.78 (m, 1H, Benzim-H4), 8.60 (s, 1H,
Benzim-H2). 13 C NMR (100 MHz, DMSO-d6): δ = 23.6, 33.1, 110.6, 120.1, 122.7, 123.7, 123.9, 126.3, 126.4,
126.5, 127.9, 128.2, 128.4, 128.5, 128.6, 130.3, 130.6, 131.1, 131.2, 132.7, 134.4, 135.7, 135.9, 136.9, 143.2, 143.8
(Benzim-C2), 146.3 (Im-C2), 148.7 (=C-Pri). Anal. Calcd. For C37 H30 N4 : C 83.74, H 5.70, N 10.56; Found,
C 83.4I, H 5.55, N 11.34.
738

GHASEMI et al./Turk J Chem
3.1.23. 1-{4-[2-(4-Chlorophenyl)-4,5-diphenyl-1H -imidazol-1-yl]phenyl} -1H -benzo [d]imidazole
(5d)
Yield: 0.35 g (67%); pale yellow solid; mp 274–276 ◦ C; FTIR (KBr): ν¯ 3057, 1511, 1227, 838, 696 cm−1 1 H
;
NMR (400 MHz, DMSO-d6): δ 7.18–7.21 (m, 1H, Benzim-H5), 7.24–7.28 (m, 2H, Ar-H), 7.31–7.35 (m, 7H,
Ar-H), 7.41–7.57 (m, 9H, Ar-H), 7.70 (d, J = 8.7 Hz, 2H, Ar-H), 7.77 (d, J = 7.8 Hz, 1H, Benzim-H4), 8.58
(s, 1H, Benzim-H2). 13 C NMR (100 MHz, DMSO-d6): δ 110.6, 120.1, 122.7, 123.7, 123.9, 126.4, 126.6, 128.2,
128.4, 128.6, 128.7, 129.1, 130.0, 130.1, 130.5, 131.2, 131.6, 132.7, 133.3, 134.1, 135.4, 136.1, 137.1, 143.2, 143.8
(Benzim-C2), 145.1 (Im-C2). Anal. Calcd. For C34 H23 ClN4 : C 78.08, H 4.43, N 10.71; Found, C 77.83, H
4.18, N 10.49.
3.1.24. 1-{4-[4,5-Diphenyl-2-(4-methoxyphenyl)-1H -imidazol-1-yl]phenyl} -1H -benzo[d]imidazole
(5e)
Yield: 0.38 g (73%); pale yellow solid; mp 242–244 ◦ C; FTIR (KBr): ν¯ 3057, 2996, 1606, 1515, 1485, 1251
cm−1 1 H NMR (400 MHz, DMSO-d6): δ 3.73 (s, 3H, OCH3), 6.89 (d, J = 8.8 Hz, 2H, Ar-H), 7.16–7.19
;
(m, 1H, Benzim-H5), 7.23–7.33 (m, 9H, Ar-H), 7.39 (d, J = 8.8 Hz, 2H, Ar-H), 7.50–7.54 (m, 5H, Ar-H), 7.68
(d, J = 8.5 Hz, 2H, Ar-H), 7.77 (d, J = 7.6 Hz, 1H, Benzim-H4), 8.56 (s, 1H, Benzim-H2). 13 C NMR (100
MHz, DMSO-d6): δ 55.1 (OCH3), 110.6, 113.8, 120.1, 122.7, 123.7, 123.8, 126.4, 126.5, 128.2, 128.5, 128.6,
129.9, 130.4, 130.5, 130.9, 131.2, 132.7, 134.4, 135.8, 135.9, 136.7, 143.2, 143.9 (Benzim-C2), 146.3 (Im-C2),
159.3 (=C-OMe). Anal. Calcd. For C35 H26 N4 O: C 81.06, H 5.05, N 10.80; Found, C 81.35, H 5.28, N 10.51.
3.1.25. 1-{4-[2-(3-Bromophenyl)-4,5-diphenyl-1H -imidazol-1-yl]phenyl} -1H -benzo [d]imidazole
(5f)
Yield: 0.39 g (70%); pale yellow solid; mp 240–242 ◦ C; FTIR (KBr): ν¯ 3054, 1508, 1451, 1283, 703 cm−1 1 H
;
NMR (400 MHz, DMSO-d6): δ 7.18–7.36 (m, 11H, Ar-H), 7.42 (d, J = 7.8 Hz, 1H, Benzim-H7), 7.51–7.61 (m,
7H, Ar-H), 7.71 (d, J = 8.4 Hz, 2H, Ar-H), 7.77 (d, J = 7.8 Hz, 1H, Benzim-H4), 8.57 (s, 1H, Benzim-H2). 13 C
NMR (100 MHz, DMSO-d6): δ 110.5, 120.1, 121.5, 122.7, 123.7, 124.2, 126.4, 126.7, 127.1, 128.2, 128.7, 128.8,
130.0, 130.5, 130.6, 130.8, 131.1, 131.2, 131.8, 132.4, 132.8, 134.1, 135.4, 136.2, 137.3, 143.1, 143.8 (Benzim-C2),
144.5 (Im-C2). Anal. Calcd. For C34 H23 BrN4 : C 71.96, H 4.09, N 9.87; Found, C 71.63, H 4.28, N 9.59.
4. Conclusion
We have described the synthesis of new 1,2,4,5-tetrasubstituted derivatives of imidazole possessing another
azole ring in the presence of Bi(NO3)3 .5H2 O-SiO2 as a heterogeneous Lewis acid catalyst. One-pot four-
component condensations of benzil, ammonium acetate, aromatic aldehydes and 4-azolyl-anilines under solvent-
free conditions at 110 ◦ C for 24 h afforded the desired products with easy workup and in good yields.
Acknowledgments
The authors gratefully acknowledge the Iran National Science Foundation (INSF) for financial support. The
research work of the University of Tabriz is also gratefully appreciated.
739

GHASEMI et al./Turk J Chem
Supplementary Material
IR, 1 H NMR, and 13 C NMR spectra of imidazole derivatives 3–5 are given at the end of this paper.
References
1. Zhang, L.; Peng, X. M.; Damu, G. L. V.; Geng, R. X.; Zhou, C. H. Med. Res. Rev. 2014, 34, 340-437.
2. Laufer, S. A.; Hauser, D. R. J.; Domeyer, D. M.; Kinkel, K.; Liedtke, A. J. J. Med. Chem. 2008, 51, 4122-4149.
3. Takle, A. K.; Brown, M. J. B.; Davies, S.; Dean, D. K.; Francis, G.; Gaiba, A.; Hird, A. W.; King, F. D.; Lovell,
P. J.; Naylor, A. Bioorg. Med. Chem. Lett. 2006, 16, 378-381.
4. Antolini, M.; Bozzoli, A.; Ghiron, C.; Kennedy, G.; Rossi, T.; Ursini, A. Bioorg. Med. Chem. Lett. 1999, 9,
1023-1028.
5. Wang, L.; Woods, K. W.; Li, Q.; Barr, K. J.; McCroskey, R. W.; Hannick, S. M.; Gherke, L.; Credo, R. B.; Hui,
Y. H.; Marsh, K. J. Med. Chem. 2002, 45, 1697-1711.
6. Callahan, J. F.; Burgess, J. L.; Fornwald, J. A.; Gaster, L. M.; Harling, J. D.; Harrington, F. P.; Heer, J.; Kwon,
C.; Lehr, R.; Mathur, A. J. Med. Chem 2002, 45, 999-1001.
7. Jez˙ewski, A.; Hammann, T.; Cywin´ski, P. J.; Gryko, D. T.; J. Phys. Chem. B, 2015, 119, 2507-2514.
8. Dierschke, F.; Mu¨llen, K. Macromol. Chem. Phys. 2007, 208, 37-43.
9. Kounavi, K. A.; Papatriantafyllopoulou, C.; Tasiopoulos, A. J.; Perlepes, S. P.; Nastopoulos, V. Polyhedron 2009,
28, 3349-3355.
10. Hahn, F. E.; Jahnke, M. C. Angew. Chem. In. Ed. 2008, 47, 3122-3172.
11. Hasaninejad, A.; Zare, A.; Shekouhy, M. J. Comb. Chem. 2010, 12, 844-849.
12. Samai, S.; Nandi, G. C.; Singh, P.; Singh, M. S. Tetrahedron 2009, 65, 10155-10161.
13. Balalaie, S.; Arabanian, A. Green Chem. 2000, 2, 274-276.
14. Karimi, A. R.; Alimohammadi, Z.; Amini, M. M. Mol. Divers. 2010, 14, 635-641.
15. Das-Sharma, S.; Hazarika, P.; Konwar, D. Tetrahedron Lett. 2008, 49, 2216-2220.
16. Kantevari, S.; Vuppalapati, S. V. N.; Biradar, D. O.; Nagarapu, L. J. Mol. Catal. A: Chem. 2007, 266, 109-113.
17. Gelens, E.; De Kanter, F.; Schmitz, R.; Sliedregt, L.; Van Steen, B.; Kruse, C. G.; Leurs, R.; Groen, M.; Orru, R.
Mol. Divers. 2006, 10, 17-22.
18. Khan, K.; Siddiqui, Z. N. Ind. Eng. Chem. Res, 2015, 54, 6611-6618.
19. Safa, K. D.; Allahvirdinesbat, M.; Namazi, H.; Nakhostin Panahi, P. C. R. Chimie 2015, 18, 883-890.
20. Aziizi, N.; Manochehri, Z.; Nahayi, A.; Torkashvand, S. J. Mol. Liq. 2014, 196, 153-158.
21. Bothwell, J. M.; Krabbe, S. W.; Mohan, R. S. Chem. Soc. Rev. 2011, 40, 4649-4707.
22. Bandyopadhyay, D.; Maldonado, S.; Banik, B. K. Molecules 2012, 17, 2643-2662.
23. Chari, M. A.; Shobha, D.; Kumar, T. K.; Dubey, P. K. ARKIVOC 2005, (xv), 74-80.
24. Jin, Z. Nat. Prod. Rep. 2006, 23, 464-496.
25. Kumar, D.; Thomas, K. R. J. J. Photochem. Photobiol A 2011, 218, 162-173.
26. Takagi, K.; Kusafuka, K.; Ito, Y.; Yamauchi, K.; Ito, K.; Fukuda, R.; Ehara, M. J. Org. Chem. 2015, 80, 7172-7183.
27. Kulh´anek, J., Bureˇs, F., Pytela, O., Mikysek, T., Ludv´ık, J. Chem. Asian J. 2011, 6, 1604-1612.
28. Ghasemi, Z.; Kalantar-Esfangare, H. Heterocycl. Commun. 2015, 21, 37-41.
29. Ghasemi, Z.; Golamhoseini Nazari, M.; Allahvirdinesbat, M.; Saraei, M.; Shahrisa, A. Lett. Org. Chem. 2012, 9,
677-682.
30. Shahrisa, A.; Ghasemi, Z.; Saraei, M. J. Heterocycl. Chem. 2009, 46, 273-277.
740

GHASEMI et al./Turk J Chem
31. Ghasemi, Z.; Farshbaf-Orafa, F.; Pirouzmand, M.; Zarrini, G.; Nikzad-Kojanag, B.; Salehi, R. Tetrahedron Lett.
2015, 56, 6393-6396.
32. Ghasemi, Z.; Shahi-Shahrak, N.; Jalali-Roomi, B.; Zakeri, Z. J. Chem. Res. 2015, 39, 73-75.
33. Safari, J.; Gandomi-Ravandi, S.; Naseh, S. J. Chem. Sci. 2013, 125, 827-833.
34. Hingane, D. G.; Shumaila, A. M. A.; Kusurkar, R. S. Indian J. Chem. 2013, 52B, 1161-1165.
35. Aghapoor, K.; Ebadi-Nia, L.; Mohsenzadeh, F.; Mohebi-Morad, M.; Balavar, Y.; Darabi, H. R. J. Organomet.
Chem. 2012, 708, 25-30.
36. Safari, J.; Dehghan-Khalili, S.; Banitaba, S. H. Synth. Commun. 2011, 41, 2359-2373.
¨
37. Ku¨c¸u¨kbay, H.; S¸ireci, N.; Yılmaz, U.; Akkurt, M.; Yalc¸ın, S. P.; Tahir, M. N.; Ott, H. Appl. Organometal. Chem.
2011, 25, 255-261.
¨
38. Ku¨c¸u¨kbay, H.; Yılmaz, U.; Akkurt, M.; Bu¨yu¨kgu¨ngo¨r, O. Turk. J. Chem. 2015, 39, 108-120.
741

Supporting Information
Bismuth (III)-SiO2 catalyzed synthesis of polysubstituted imidazoles with the
participation of azaaryl derivatives of aniline in four component reactions
Zarrin Ghasemi*, Ziba Zakeri and Maryam Allahvirdinesbat
O
O
NH2
+
NH4OAc
Bi(NO3)3.5H2O-SiO2
110oC
X
N
N
Y
N
X
H
O
Y
N
R1
R1
R2
R2
R2= H, 4-Me, 4-CH(Me)2, 4-OMe,4-Cl, 3-Br, ...
X=CH, Y=N, R1=H
X=CH, Y=N, R1=H
X=N, Y=CH, R1=H
25 Examples
X=N, Y=CH, R1=3-Me
Experimental section
General
Melting points were determined on a Electrothermal MEL-TEMP apparatus (model 1202D) and are
1
uncorrected. FT-IR spectra were obtained with a Bruker Tensor 27 spectrometer; ν in cm-1. H and 13C
NMR spectra were recorded with a Bruker Spectrospin Avance 400 spectrometer operating at 400 MHz
and 100 MHz respectively, in DMSO-d6; chemical shifts are given in parts per million (ppm, δ) relative to
residual solvent peaks as standard at 298 ºK (2.50 ppm (1H), 39.5 ppm (13C)); J in Hz. Elemental analyses
were measured by Vario EL ΙΙΙ apparatus (Elementar Co.). Microwave experiment was conducted in a
Milestone MicroSYNTH apparatus. Ultrasonic mediated experiments were carried out by used of an
ultrasonic processor probe (SONOPULS Ultrasonic homogenizers). The used silica gel cocatalyst was
Kieselgel 60 (0.040-0.063 mm, Merk: 9385).
1

1- Synthesis of aniline derivatives 2a-d; General procedure: A mixture of nitrobenzene
derivatives 1a-d (5 mmol), zinc powder (3.26 g, 50 mmol), acetic acid (4 mL) and ethanol (7 mL)
was stirred at 70 oC for 1.5 h. The hot reaction mixture was then filtered and the solid was washed
with hot EtOH (5 mL). The combined filtrate was concentrated, neutralized with aq. NaHCO3 and
then extracted with EtOAc (3×8 mL). The organic layers were combined, washed with water (20
mL), dried over Na2SO4 and concentrated to dryness. The residue yellow solid was used as amine
partner in four component reactions.
Zn/CH3CO2H, EtOH,
N
NO2
N
NH2
70 oC
1a-d
2a-d
Amine 2a-d
Yield (%)
m.p. (oC)
N
140-142
117-119
Imidazol-1-yl
2a
2b
65
69
Benzimidazol-1-yl
46-48
88-90
Pyrazol-1-yl
2c
65
68
3-Methylpyrazol-1-yl
2d
For references about the other preparation methods and m.p. value of amine 2a see: (a) Yongbin,
W.; Yu, Z.; Beibei, Y.; Ao, Z.; Qizheng, Y. Org. Biomol. Chem. 2015, 13, 4101. (b) Ying-Lei, W.; Jun,
L.; Zu-Liang, L. J. Chinese Chem. Soc. 2013, 60, 1007. (c) Wen, C.; Yuanyuan, Z.; Liangbo, Z.; Jingbo,
L.; Rugang, X.; Jingsong, Y. J. Am. Chem. Soc. 2007, 129, 13879. (d) Engel-Andreasen, J.; Shimpukade,
B.; Ulven, T. Green Chem. 2013, 15, 336. (e) Hosseini-Sarvari, M.; Moeini, F. RSC Adv. 2014, 4, 7321.
(f) Cheung, C. W.; Surry, D. S.; Buchwald, S. L. Org. Lett. 2013, 15, 3734. (g) Zhang, Z.; Mao, J.; Zhu,
D.; Wu, F.; Chen, H.; Wan, B. Tetrahedron 2006, 62, 4435.
2

Figure S1. FTIR (KBr) spectrum of compound 2a.
For references about the other preparation methods and m.p. value of amine 2b see: (a) Smallheer,
J. M.; Alexander, R. S.; Wang, J.; Wang, S.; Nakajima, S.; Rossi, K. A.; Smallwood, A.; Barbera, F.;
Burdick, D.; Luettgen, J. M.; Knabb, R. M.; Wexler, R. R.; Jadhav, P. K. Bioorg. Med. Chem. Lett. 2004,
14, 5263. (b) Jose, E.; Manuel, G.; Nerea, I.; Carmen, P.; Mar, R. Appl. Spectroscopy 1995, 49, 1111. (c)
Gale, D. J.; Wilshire, J. F. K. Austr. J. Chem. 1970, 23, 1063.
Figure S2. FTIR (KBr) spectrum of compound 2b.
3

For references about the other preparation methods and m.p. value of amine 2c see: (a) De La Hoz,
A.; Diaz-Ortiz, A.; Elguero, J.; Martinez, L. J.; Moreno, A.; Sanchez-Migallon, A. Tetrahedron 2001, 57,
4397. (b) Cristau, H. J; Cellier, P. P.; Spindler, J. F.; Taillefer, M. Eur. J. Org. Chem. 2004, 4, 695. (c)
Taillefer, M.; Xia, N.; Ouali, A. Angew. Chem. Int. Ed. 2007, 46, 934. (d) Lee, H. W.; Chan, A. S. C.;
Kwong, F. Y. Tetrahedron Lett. 2009, 50, 5868. (e) Huang, M.; Lin, X.; Zhu, X.; Peng, W.; Xie, J.; Wan,
Y. Eur. J. Org. Chem. 2011, 24, 4523. (f) Jia, Z. J.; Wu, Y.; Huang, W.; Zhang, P.; Clizbe, L. A.;
Goldman, E. A.; Sinha, U.; Arfsten, A. E.; Edwards, S. T.; Alphonso, M.; Hutchaleelaha, A.;
Scarborough, R. M.; Zhu, B. Y. Bioorg. Med. Chem. Lett. 2004, 14, 1221.
Figure S3. FTIR (KBr) spectrum of compound 2c.
For references about the other preparation methods and m.p. value of amine 2d see: (a)
Bouchet, P.; Coquelet, C.; Joncheray, G.; Elguero, J. Synth. Commun. 1974, 4, 57. (b) Burness, D. M.
J. Org. Chem. 1956, 21, 102.
4

Figure S4. FTIR (KBr) spectrum of compound 2d.
Figure S5: 1H NMR (400 MHz) spectrum of compound 2d in DMSO-d6.
5

Figure S6: Expanded 1H NMR (400 MHz) spectrum of compound 2d in DMSO-d6.
Figure S7: 13C NMR (100 MHz) spectrum of compound 2d in DMSO-d6.
6

2- Synthesis of substituted imidazoles 3-5; General procedure: A mixture of N-(4-aminophenyl)
azoles 2a-d (1 mmol), benzil (1 mmol, 0.21 g), aromatic aldehyde (1 mmol) and ammonium
acetate (1 mmol, 0.077 g) was stirred vigorously. Bi(NO3)3.5H2O (0.15 mmol, 0,073 g, 15 mol%)
and SiO2 (0.5 g) were mixed effectively and added to the mixed reactants. The resulting mixture
o
was heated at 110 C for 24 h. Acetone (50 mL) was then added and the mixture was stirred at
o
50 C for 10 min. Filtering the hot mixture and then concentration of the filtrate, produced the
crude product. Recrystallization of the crude products in EtOH 96% gave the desired product 3-
5.
2-1-
1-[4-(3-Methyl-1H-pyrazol-1-yl)phenyl]-2,4,5-triphenyl-1H-imidazole (3a): Pale
ο
yellow solid; Yield 0.35 g (78%) mp 244-246 C. FTIR (KBr): ῡ 3054, 2925, 1517, 1475, 846,
693 cm-1; 1H NMR (DMSO-d6): 2.23 (s, 3H, CH3), 6.32 (d, J= 2.4 Hz, 1H, Py-H4), 7.17-7.35 (m,
13H, Ar-H), 7.43-7.44 (m, 2H, Ar-H), 7.50 (d, J=7.9 Hz, 2H, Ar-H), 7.72 (d, J= 8.8 Hz, 2H, Ar-
H), 8.37 (d, J= 2.4 Hz, 1H, Py-H5). 13C NMR (DMSO-d6): δ=13.4, 108.3 (Py-C4), 117.9, 126.4,
126.5, 128.1, 128.2, 128.3, 128.4, 128.5, 128.52, 129.8, 130.3, 130.34, 131.1, 131.3, 133.7, 134.3,
136.8, 139.2, 146.1 (Im-C2), 150.2 (Py-C3). Anal. Calcd. For C31H24N4: C, 82.27; H, 5.35; N,
12.38; Found: C, 81.98; H, 5.12; N, 12.55%.
Figure S8. FTIR (KBr) spectrum of compound 3a.
7

Figure S9: 1H NMR (400 MHz) spectrum of compound 3a in DMSO-d6.
Figure S10: Expanded 1H NMR (400 MHz) spectrum of compound 3a in DMSO-d6.
8

Figure S11: 13C NMR (100 MHz) spectrum of compound 3a in DMSO-d6.
Figure S12: Expanded 13C NMR (100 MHz) spectrum of compound 3a in DMSO-d6.
9

2-2-
4,5-Diphenyl-1-[4-(3-methyl-1H-pyrazol-1-yl)phenyl]-2-(p-tolyl)-1H-imidazole (3b): Yield:
0.32 g (70%); pale yellow solid; m.p. 212-214 οC; FTIR (KBr): ῡ 3049, 2924, 1522, 1362, 1035 cm-1; 1H
NMR (400 MHz, DMSO-d6): δ 2.23 (s, 3H, CH3), 2.26 (s, 3H, CH3), 6.33 (s, 1H, Py-H4), 7.11-7.34 (m,
14H, Ar-H), 7.48 (d, J=7.5 Hz, 2H, Ar-H), 7.71 (d, J=8.6 Hz, 2H, Ar-H), 8.37 (s, 1H, Py-H5). 13C NMR
(100 MHz, DMSO-d6): δ 13.4, 20.8, 108.3 (Py-C4), 117.2, 126.3, 126.5, 127.5, 128.2, 128.3, 128.4,
128.6, 128.8, 129.9, 130.4, 131.2, 133.8, 134.4, 136.7, 137.9, 139.2, 150.2 (Py-C3). Anal. Calcd. For
C32H26N4: C 82.38, H 5.62, N 12.01; Found, C 82.15, H 5.39, N 12.34.
Figure S13. FTIR (KBr) spectrum of compound 3b.
10

Figure S14: 1H NMR (400 MHz) spectrum of compound 3b in DMSO-d6.
Figure S15: Expanded 1H NMR (400 MHz) spectrum of compound 3b in DMSO-d6.
11

Figure S16: 13C NMR (100 MHz) spectrum of compound 3b in DMSO-d6.
2-3-
2-(4-Isopropylphenyl)-1-[4-(3-methyl-1H-pyrazol-1-yl)phenyl]-4,5-Diphenyl-1H-imidazole
ο
(3c): Yield: 0.34 g (69%); pale yellow solid; m.p. 218-219 C; FTIR (KBr): ῡ 3046, 2957, 1522, 1361,
1
840, 654 cm-1; H NMR (400 MHz, DMSO-d6): δ 1.15 (d, J=6.9 Hz, 6H, (CH3)2CH), 2.23 (s, 3H, CH3),
2.82 (m, 1H, CH(Me)2), 6.33 (d, J=2.2 Hz, 1H, Py-H4), 7.17-7.37 (m, 14H, Ar-H), 7.49 (d, J= 7.3 Hz,
13
2H, Ar-H), 7.73 (d, J= 8.7 Hz, 2H, Ar-H), 8.37 (d, J=2.3 Hz, 1H, Py-H5). C NMR (100 MHz, DMSO-
d6): δ 13.4, 23.6, 33.1, 108.3 (Py-C4), 117.9, 126.2, 126.3, 126.4, 127.9, 128.1, 128.2, 128.4, 128.5,
129.9, 130.4, 131.1, 131.2, 133.8, 134.4, 136.7, 139.2, 146.1 (Im-C2), 148.6 (=C-iPr), 150.2 (Py-C3).
Anal. Calcd. For C34H30N4: C 82.56, H 6.11, N 11.33; Found, C 82.29, H 6.34, N 11.65.
12

Figure S17: FTIR (KBr) spectrum of compound 3c.
Figure S18: 1H NMR (400 MHz) spectrum of compound 3c in DMSO-d6.
13

Figure S19: Expanded 1H NMR (400 MHz) spectrum of compound 3c in DMSO-d6.
Figure S20: 13C NMR (100 MHz) spectrum of compound 3c in DMSO-d6.
14

2-4-
2-(4-methoxyphenyl)-1-[4-(3-methyl-1H-pyrazol-1-yl) phenyl]-4,5-diphenyl-1H-imidazole
(3d): Yield: 0.328 g (70%); pale yellow solid; mp 224-226 οC; FTIR (KBr): ῡ 3048, 2929, 1607, 1523,
1248, 944 cm-1. 1H NMR (400 MHz, DMSO-d6): δ=2.23 (s, 3H, CH3), 3.72 (s, 3H, OCH3), 6.33 (s, 1H,
Py-H4), 6.87 (d, J=8.5 Hz, 2H, Ar-H), 7.15-7.37 (m, 12H, Ar-H), 7.49 (d, J=7.9 Hz, 2H, Ar-H), 7.72 (d,
J=8.5 Hz, 2H, Ar-H), 8.37 (s, 1H, Py-H5). 13C NMR (100 MHz, DMSO-d6): δ=13.4, 55.1 (OCH3), 108.3
(Py-C4), 113.7, 117.9, 122.7, 126.3, 126.4, 128.2, 128.4, 128.5, 129.7, 129.9, 130.5, 130.9, 131.2, 133.9,
134.5, 136.6, 139.2, 146.1 (Im-C2), 150.2 (Py-C3), 159.3 (=C-OMe). Anal. Calcd. For C32H26N4O: C
79.64, H 5.43, N 11.61; Found, C 79.32, H 5.19, N 11.87.
Figure S21. FTIR (KBr) spectrum of compound 3d.
15

Figure S22: 1H NMR (400 MHz) spectrum of compound 3d in DMSO-d6.
Figure S23: Expanded 1H NMR (400 MHz) spectrum of compound 3d in DMSO-d6.
16

Figure S24: 13C NMR (100 MHz) spectrum of compound 3d in DMSO-d6.
Figure S25: Expanded 13C NMR (100 MHz) spectrum of compound 3d in DMSO-d6.
17