Application of various types of alumina and nano-γ- Alumina sulfuric acid in the synthesis of α-aminonitriles derivatives: Comparative study

Article abstract of DOI:10.4314/bcse.v28i3.13

An efficient and green protocol for the synthesis of α-aminonitrile derivatives by one-pot reaction of different aldehydes with amines and trimethylsilyl cyanide has been developed using natural alumina, alumina sulfuric acid (ASA), nano-γ-alumina, nano-γ

Full text of DOI:10.4314/bcse.v28i3.13

Bull. Chem. Soc. Ethiop. 2014, 28(3), 441-450.
Printed in Ethiopia
DOI: http://dx.doi.org/10.4314/bcse.v28i3.13
ISSN 1011-3924
 2014 Chemical Society of Ethiopia
APPLICATION OF VARIOUS TYPES OF ALUMINA AND NANO-γ-ALUMINA
SULFURIC ACID IN THE SYNTHESIS OF α-AMINONITRILES DERIVATIVES:
COMPARATIVE STUDY
1
,*
2,3
1
Abbas Teimouri , Leila Ghorbanian and Athar Moatari
1
Chemistry Department, Payame Noor University, 19395-3697, Tehran, Iran
2
Torabinejad Dental Research Center and Department of Oral and Maxillofacial Pathology,
School of Dentistry, Isfahan University of Medical Sciences, Isfahan, Iran
3
Materials Engineering Department, Isfahan University of Technology, Isfahan, Iran
(
Received August 29, 2013; revised May 14, 2014)
ABSTRACT. An efficient and green protocol for the synthesis of α-aminonitrile derivatives by one-pot reaction
of different aldehydes with amines and trimethylsilyl cyanide has been developed using natural alumina, alumina
sulfuric acid (ASA), nano-γ-alumina, nano-γ-alumina sulfuric acid (nano-γ-ASA) under microwave irradiation and
solvent-free conditions. The advantages of methods are short reaction times, high yields, milder conditions and
easy work up. The catalysts can be recovered for the subsequent reactions and reused without any appreciable loss
of efficiency.
KEY WORDS: Nano-γ-alumina, Nano-γ-alumina sulfuric acid, Green synthesis, Microwave irradiation, α-
aminonitriles derivatives
INTRODUCTION
α-Aminonitriles are significantly important intermediates for the synthesis of a wide variety of
amino acids, amides, diamines, and nitrogen-containing heterocycles [1]. Among the methods
reported for the synthesis of α-aminonitriles, nucleophilic addition of cyanide ion to imines
(
Strecker reaction), is of great importance to modern organic chemistry as it offers one of the
most direct and viable methods for the synthesis of α-aminonitriles [2].
Thus, several modifications of the Strecker reaction have been developed using a variety of
cyanide reagents such as alkaline cyanides [3], Et AlCN [4], (EtO) -POCN [5], Zn(CN) [6],
2
2
2
3 4 6
HCN [7], Bu SnCN [8], TMSCN [9], K [Fe(CN) ] [10], along with catalysts variant such as
InCl [11], BiCl [12], RhI [13], NiCl [14], RuCl [15], montmorillonite KSF clay [16], silica
3
3
3
2
3
sulfuric acid [17], silica-supported heteropoly acids [18], silica-bonded sulfamic acid [19],
silica-based ionic liquids [20], I [21], xanthan sulfuric acid [22], Zr-MCM-41 nanoreactors
4
23], Zr-Cu(OTf) [24], K PdCl [25], Al-MCM-41 [26] and Ga-TUD-1 [27] under various
2
[
2
2
reaction conditions homogeneously catalyze the Strecker-type reaction.
However, many of these methods require the use of expensive reagents, harsh conditions,
extended reaction times, and also require tedious work-up that generates a large amount of toxic
waste. In order to overcome these problems, recently one-pot procedures have been developed
for this transformation [28].
Performance of chemical reactions under solvent-free condition is one of the best methods
for the protection of environment from toxic and hazardous organic solvents, thus the solvent-
free condition is one of the ways to green chemistry [29].
In the recent years, the use of nano-γ-alumina and heterogeneous solid acid catalysts such as
alumina sulfuric acid [30] and nano-γ-alumina sulfuric [31] have been received considerable
interest to chemists due to their eco-friendly, easy preparation in nano-size, reusability and
recovery, low cost, and high acid strength. These catalysts are actually sulfuric acid linked to
alumina surface via covalent bond without the risks and disadvantages of sulfuric acid; such as
_
*
_________
Corresponding author. E-mail: a_teimouri@pnu.ac.ir

442
Abbas Teimouri et al.
nonreusability, waste production and scale-up problems. A question may rise here is what type
of alumina is more effective in synthesis of α-aminonitriles compounds.
In continuation of our investigations on the use of novel synthetic methodologies in a
heterogeneous system through multi-component procedures [32, 33], here we present our recent
studies on the synthesis of α-aminonitriles derivatives by one-pot reaction of different aldehydes
with amines and trimethylsilyl cyanides in the presence of natural alumina, alumina sulfuric
acid, nano-γ-alumina, nano-γ-alumina sulfuric under microwave irradiation and solvent-free
conditions.
RESULTS AND DISCUSSION
In an effort to develop an optimal catalytic system, various reaction parameters like effect of
catalyst loading, and time for the preparation of α-aminonitriles derivatives were studied. The
results listed in Table 1 showed that the conversions were sensitive to the catalyst type. The
results showed that nano-γ-alumina sulfuric acid promoted the reaction more effective than
alumina sulfuric acid, nano-γ-alumina as far as the amount of catalyst and reaction times are
concerned (Table 1, entry 3).
One reason for increase the catalytic activity may be related to the number of available
active sites. In order to evaluate the effect of the catalyst particle size on the catalytic activity,
the results were compared with those obtained using alumina sulfuric acid (ASA). No good
activity was observed in the presence of alumina sulfuric acid or natural alumina (Table 1,
entries 7 and 15). In comparison with conventional methods, microwave irradiation reactions are
cleaner and microwave irradiation decreased remarkably the reaction times. No side products
were detected in these reactions. Microwave irradiation affords the respective products in only
5
–10 min (see Table 1). 10% of the expected product was obtained in the absence of catalyst. To
further improve the yield and to optimize the reaction conditions, the same reaction was carried
out in the presence of (10 mg) of catalyst under similar conditions. Reaction with 10 mg of the
catalyst required a longer reaction time and the yield of product was dramatically increased up
to 85% after irradiating the mixture for only 10 min.
a
Table 1. Effect of catalyst type and amount of catalyst on the synthesis of α-aminonitrile derivatives .
b
Entry
Catalyst
Catalyst loading (mg)
Time (min)
Yield (%)
10
1
2
3
4
5
6
7
8
9
-
120
10
5
5
5
10
5
5
5
10
5
5
5
10
5
Nano-ASA
10
15
20
25
10
15
20
25
10
15
20
25
10
15
20
25
85
96
84
76
75
84
76
72
68
73
66
65
60
65
58
54
Alumina-sulfuric acid
Nano-γ-alumina
1
1
1
1
1
1
1
1
0
1
2
3
4
5
6
7
Natural alumina
5
5
a
b
Bezaldehyde (1 mmol), aniline (1 mmol) and trimethylsilyl cyanide (1.5 mmol). Yields after isolation of
products.
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Application of various types of alumina and nano-γ-alumina sulfuric acid
443
To minimize the formation of by-products and to achieve good yield of the desired product,
the reaction is optimized by varying the amount of catalyst (15, 20 and 25 mg). An increase in
the amount of nano-ASA from 10 to 15 mg increased the yield of the desired product to a great
extent (85–96%). The percentage yield of the product with 10, 15, 20 and 25 mg of alumina
sulfuric acid as the catalyst are 85%, 96%, 84% and 76%, respectively (Table 1, entries 6-9).
For the nano-γ-alumina and natural alumina as the catalyst, when the catalyst content was
increased to 25 mg, the product yield decreased to 65% (Table 1, entry 13) and 54% (Table 1,
entry 17), respectively. Therefore, it was found that the use of 15 mg of the catalyst was
sufficient to promote the reaction, and higher amounts of the catalyst did not increase the yields
significantly. The temperature and the MW power were also optimized and the best results were
o
obtained using 15 mg of nano-ASA at 90 C and microwave power (600 W). No increase in
0
yield was observed at higher temperatures, while lowering the temperature below 90 C reduced
the reaction rate.
On reaching the optimized conditions a wide range of α-aminonitriles were synthesized by
using aromatic aldehydes with electron-donating or electron-withdrawing groups. The results
are shown in Table 2. Most of the aldehydes reacted efficiently with aniline and TMSCN to
furnish the corresponding products 1a–g in excellent yields (65-96%).
a
Table 2. Acid-catalyzed synthesis of α-aminonitriles derivatives under microwave irradiation and solvent-
free conditions.
Ar
CN
Catalyst
Ar CHO
+
Ph NH
2
+
TMSCN
0
MW (600 W), 90 C
NHPh
b
o
Entry/
Ar
Time (min)/Yield (%)
MP C (lit.) [Ref.]
Product
Natural
alumina
12/65
12/62
12/65
12/64
12/64
12/62
12/60
nano-γ-
alumina
12/73
12/65
12/69
12/70
12/72
12/65
12/69
Alumi nano-γ-
na-SA ASA
1
2
3
4
5
6
7
(1a)
(1b)
(1c)
(1d)
(1e)
(1f)
(1g)
Ph
12/84
12/85
12/85
12/86
12/89
12/86
12/84
12/96
72-74 (75-76) [13]
90-92
120-122 (120-122) [25]
70-72 (74-76) [27]
94-96 (92-94) [27]
108-110 (108-110) [13]
4-NO
2
C
6
H
5
12/93
12/90
12/91
12/93
12/92
12/92
4-OHC
6
H
5
4-CH
4-OCH
4-ClC
4-BrC
3 6 5
C H
3
C
6
H
5
5
6
H
6
H
5
100-102 (101-103) [19]
b
a
bezaldehyde (1 mmol), aniline (1 mmol) and trimethylsilyl cyanide (1.5 mmol). Isolated yields of products
characterized by IR, H NMR, and mass spectroscopy.
1
Table 3. Comparison of the efficiency of nano-ASA with other reported catalysts in the synthesis of α-
a
aminonitriles derivatives .
b
Entry
Condition
Time (min)
Yield (%)
References
1
2
3
4
5
6
7
8
Nano-ASA
12
8
96
88
84
92
90
95
94
This work
K
4
[Fe(CN)
BiCl /CH CN, rt
NiCl /CH CN, rt
K10/CH Cl
Al-MCM-41/CH
/CH CN, rt
Ga-TUD-1/solvent-free, rt
6
], EtOH
10
12
14
16
18
21
27
3
3
10
12
3.5
24
1
2
3
2
2
2 2
Cl
I
2
3
0.5
95
a
b
Aldhyde, amine and trimethylsilyl cyanide in the presence of catalyt. Isolated yields.
Bull. Chem. Soc. Ethiop. 2014, 28(3)

444
Abbas Teimouri et al.
Table 3 compares the efficiency of present method with the efficiency of other methods in
the synthesis of α-aminonitriles derivatives. As evident from Tables 3, nano-γ-alumina sulfuric
acid shows better efficiency than other methods.
A proposed mechanism for the rule of various types of alumina catalysts in the reaction of
aromatic aldehyde, amine and trimethylsilyl cyanide is presented in Figure 1.
We propose a mechanism for the formation of α-aminonitriles derivatives 1a–g it has been
hypothesized that the reaction proceeds. First, aromatic aldehyde activated by the acidic proton
of alumina reacts with amines to form a key intermediate. Finally, nucleophilic addition of
cyanide ion to the intermediate, which is formed from condensation of aldehydes and amines,
yields α-aminonitriles derivatives.
Al
Al
Al
Al
O
O
H
O
O
O
H
O
H
N
NC
NHR
Ph
O
HO
NHPh
HO
Ar
Ph
-
H
-
3
Me SiOH
H
Ar
Ar
Me Si
H
H
Ar
H
CN
3
PhNH
2
Figure 1. Proposed mechanism for one-pot synthesis of α-aminonitriles derivatives.
Characterization
X-ray diffraction pattern were recorded on diffractometer (Philips X'pert) using Cu Kα radiation
λ = 1.5405 Å), Crystallite size of the crystalline phase was determined from the peak of
maximum intensity by using Scherrer formula with a shape factor (K) of 0.9, as below:
Crystallite size = K.λ/W.cosθ, where, W = W −W and W is the broadened profile width of
experimental sample and W is the standard profile width of reference silicon sample. FT-IR
spectra of the catalysts were recorded by FT-IR spectrophotometer in the range of 400–4000
(
b
s
b
s
−
1
−1
cm with a resolution of 4 cm by mixing the sample with KBr.
Figure 2 indicates the formation of crystallized alumina, as broad peaks indexed for γ-Al
2
O
3
o
are seen in the XRD pattern, where small and broad peaks started appearing at 2θ = 48 and at
o
2
θ = 67 . The broadening of the XRD peaks revealed the nano-size nature of γ-Al
2 3
O particles in
alumina samples.
The XRD patterns of nano-γ-alumina sulfuric acid obtained. Characteristic peaks appeared
at 2θ = 31.7, 34.5, 36.2 and 56.5 (Figure 3). The XRD patterns of the synthesized nano-γ-
alumina sulfuric acid show the crystallization of structures.
o
The FT-IR spectra of alumina samples calcined at 550 C (Figure 4) showed an intense band
-
1
-1
centered around 3500 cm and a broad band at 1640 cm , these are assigned to stretching and
bending modes of adsorbed water. The Al–O–Al bending stretching vibrations observed at
-
1
around 1125 cm are due to symmetric and asymmetric bending modes, respectively. The OH
-
1
torsional mode observed at 800 cm overlaps with Al–O stretching vibrations. The weak band at
-
1
-1
2
091 cm is assigned to a combination band. Bands observed at 480-650 cm are attributable to
stretching and bending modes of AlO [36].
6
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Application of various types of alumina and nano-γ-alumina sulfuric acid
445
The FT-IR spectra of nano-γ-alumina sulfuric acid showed peaks at 605, 889, 1010–1080
-
1
and 1120–1230 cm corresponded to asymmetric and symmetric stretching modes of SO
2
groups, that is a good reason for functionalization of nano-γ-alumina by chlorosulfonic acid. The
-
1
spectrum also shows a broad OH stretching absorption around 3000-3700 cm (Figure 4).
The morphology of the catalysts was studied. SEM micrograph nano-γ-alumina sulfuric acid
have been presented in Figure 5. The SEM picture showed that the particles were of irregular
shape with a wide size distribution. A part of the spectra data has been published in our previous
work [32].
Figure 2. XRD pattern of nano-γ-alumina catalyst.
Figure 3. XRD pattern of nano-γ-alumina sulfuric acid catalyst.
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446
Abbas Teimouri et al.
Figure 4. FT-IR spectra of a) alumina, b) alumina sulfuric acid, c) nano-γ-alumina and d) nano-
γ-alumina sulfuric acid catalysts.
Figure 5. SEM micrograph of nano-γ-alumina sulfuric acid catalyst.
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Application of various types of alumina and nano-γ-alumina sulfuric acid
447
Catalysts successfully recycled (after thorough washing and activation) with little variation
of yield. The recovery and reusability of the catalyst was investigated in the product formation.
After completion of the reaction, the catalyst was separated by filtration, washed 3 times with 5
mL acetone, then with doubly distilled water several times and dried at 110 ºC. Then the
recovered catalyst was used in the next run (Figure 6).
Figure 6. Change of the catalyst activity in the four consecutive runs.
CONCLUSIONS
In conclusion, we have demonstrated an efficient, versatile and convenient method for the
synthesis of α-aminonitriles derivatives in reaction of different aromatic aldehyde with acyl
hydrazide under microwave irradiation without solvent. A comparison of the catalytic efficiency
of natural alumina, alumina sulfuric acid, nano-γ-alumina, nano-γ-alumina sulfuric acid with the
nano-γ-alumina sulfuric acid exhibiting greater activity has also been demonstrated. Compared
to previously reported methods, Moreover, the mild reaction conditions, high yields, easy work-
up, clean reaction profiles and lower catalyst loading render this approach as an interesting
alternative to the existing methods.
EXPERIMENTAL
All reagents were purchased from Merck and used without further purification. Products were
1
13
characterized by spectroscopy data (IR, FTIR, H NMR and C NMR spectra), elemental
analysis (CHN) and melting points. The structural morphology of the samples was evaluated
using scanning electron microscope (SEM). The samples were analyzed by X-ray diffraction
(
XRD) using Philips X'PERT MPD X-ray diffractometer (XRD). A JASCO FT/IR-680 PLUS
spectrometer was used to record IR spectra using KBr pellets. NMR spectra were recorded on a
Bruker 400 Ultrasheild NMR and DMSO-d was used as solvent. Melting points reported were
6
determined by open capillary method using a Galen Kamp melting point apparatus and are
uncorrected. Mass spectra were recorded on a Shimadzu Gas Chromatograph Mass
Spectrometer GCMS-QP5050A/Q P5000 apparatus. The reactions were performed using a
microwave oven with a power of 600 W specially designed for organic synthesis.
Catalyst preparation
Preparation of alumina-sulfuric acid
The alumina-sulfuric acid was prepared according to the procedure described earlier [34]. A 500
mL suction flask was used. It was equipped with a constant pressure dropping funnel containing
freshly distilled chlorosulfonic acid (2.75 mL, 41.2 mmol) was charged with neutral alumina (10
Bull. Chem. Soc. Ethiop. 2014, 28(3)

448
Abbas Teimouri et al.
g, 100 mmol) dried at 120 °C for 2 h with stirring. Chlorosulfonic acid was added dropwise over
a period of 30 min at room temperature. The liberated HCl was removed through a CaCl drying
2
tube under reduced pressure to a water trap. Then it was kept in this condition for 1 h at room
temperature, was washed with distilled water several times, ethanol (2 times) and dried at 130
°C for 4 h.
Synthesis of nano-γ-alumina catalyst
The nano-γ-alumina was prepared by sol–gel method according to a described procedure [35].
In a typical experiment, aluminum nitrate (15.614 g) was added to 400 mL of deionized water.
Similarly solution of sodium carbonate was prepared by dissolving (7.95 g) in 400 mL of
deionized water. 200 mL of deionized water was taken in a 2 l capacity round-bottom flask and
stirred well using magnetic stirrer. Then sodium carbonate and aluminum nitrate solutions were
added to 200 mL of deionized water (from separate burettes) drop wise.
The temperature was maintained 70 °C during experiment. The pH after precipitation was
found to be in the range of 7.5–8.5. The mixture was stirred for 4 h. The digested precipitates
were filtered and re-dispersed again in hot 2 L of deionized water, filtered and finally washed
with ethanol first followed by acetone to avoid contamination of ‘Na’ ions; and air dried at room
temperature. The dried precipitates were calcined in a furnace at 550 °C for 5 h to produce nano-
sized γ-Al
2
O
3
powders.
Synthesis of nano-
γ
-ASA
For synthesis of nano-γ-ASA, in a 500 mL round-bottom flask, chlorosulfonic acid (1.35 mL)
was added dropwise to the high surface area nano-γ-alumina (5 g) over a period of 30 min at
room temperature. The components were mixed with constant stirring about 30 min at ambient
temperature to afford the nano-ASA as a uniform white solid. The liberated HCl was removed
through a CaCl drying tube under reduced pressure to a water trap. The solid phase obtained
2
was washed with distilled water several times, dried at 130 °C for 4 h.
General procedure for the synthesis of α-aminonitriles derivatives
To the reaction mixture of aldehyde (1 mmol), amine (1 mmol), trimethylsilyl cyanide (1.5
mmol) catalyst (10 mg) was subjected to microwave irradiation (600 W) at 90 °C for 15 min.
The reaction was monitored by TLC. After completion of the reaction, as indicated by TLC, the
reaction mixture was filtered and washed with EtOAc (2×20 mL and the catalyst was separated
by filtration. The organic solvent was removed under reduced pressure. After purification by
chromatography on silica gel (ethyl acetate/n-hexane 20:80) α-aminonitriles were obtained.
-
1
2
2
1
(
1
-(N-anilino)-2-phenyl acetonitrile (1a). M.p.: 72-74 °C. FTIR (KBr) (νmax, cm ): 3334, 3023,
946, 2234, 1603, 1517, 1280, 954, 750 cm . H NMR (400 MHz, DMSO-d
-1 1
6 H
): δ : 3.98 (bs,
H), 5.42 (s, 1H), 6.74 (d, J = 7.6 Hz, 2H), 6.86 (t, J = 7.4 Hz, 1H), 7.24 (t, J = 7.6 Hz, 2H), 7.40
1
3
m, 3H), 7.58 (m, 2H); C NMR (100 MHz, DMSO-d
27.29, 129.33, 129.61, 129.56, 133.99, 144.56. MS (m/z): 208.10 (M ). Anal. calcd for
: C, 80.74; H, 5.81; N, 13.45. Found: C, 80.56; H, 5.63; N, 13.32.
6 C
): δ : 49.88, 114.19, 118.14, 119.95,
+
14 12 2
C H N
-
1
2
-(4-Nitrophenyl)-2-(phenylamino) acetonitrile (1b). M.p.: 90-92 °C. FTIR (KBr) (νmax, cm ):
-1 1
3
312, 3019, 2246, 1666, 1590, 1466, 1103, 756 cm . H NMR (400 MHz, DMSO-d ): δ : 4.13
6 H
(
7
d, J = 8.0 Hz, 1H), 5.20 (d, J = 8.0 Hz, 1H), 6.64 (d, J = 8.0 Hz, 2H), 6.75 (t, J = 7.8 Hz, 1H),
.05 (t, J = 7.8 Hz, 2H), 7.52 (d, J = 8.05 Hz, 2H), 7.95 (d, J = 8.05 Hz, 2H); C NMR (100
1
3
MHz, DMSO-d
6
C
): δ : 49.31, 114.32, 115.74, 118.18, 119.46, 123.91, 127.84, 129.33, 144.89,
Bull. Chem. Soc. Ethiop. 2014, 28(3)

Application of various types of alumina and nano-γ-alumina sulfuric acid
449
+
1
56.63. MS (m/z): 253.09 (M ). Anal. calcd for C14
H
11
N
3
O
2
: C, 66.40; H, 4.38; N, 16.59.
Found: C, 66.29; H, 4.22; N, 16.43.
-
1
2
-(N-Anilino)-2-(4-hydroxyphenyl) acetonitrile (1c). M.p.: 120-122 °C. FTIR (KBr) (ν , cm ):
max
-1 1
3
6 H
344, 3029, 2236, 1606, 1263, 1157, 834, 748 cm . H NMR (400 MHz, DMSO-d ): δ : 4.53
(
br s, 1H), 5.16 (s, 1H), 6.75–6.90 (m, 5H), 7.23 (t, J = 7.4 Hz, 2H), 7.38 (d, J = 8.2 Hz, 2H),
13
9
1
7
.81 (br s, 1H); C NMR (100 MHz, DMSO-d ): δ : 49.36, 113.78, 115.65, 118.48, 119.29,
6 C
+
24.31, 128.46, 129.13, 145.39, 156.28. MS (m/z): 224.09 (M ). Anal. calcd for C14
4.98; H, 5.39; N, 12.49. Found: C, 74.71; H, 5.21; N, 12.33.
12 2
H N O: C,
-
1
2
-(N-Anilino)-2-(4-methylphenyl) acetonitrile (1d). M.p.: 70-72 °C. FTIR (KBr) (νmax, cm ):
-1 1
3
6 H
311, 3025, 2236, 1665, 1559, 1254, 1121, 761 cm . H NMR (400 MHz, DMSO-d ): δ : 2.36
(
8
s, 3H), 3.52 (bs, 1H), 5.31 (s, 1H), 6.61 (d, J = 7.6 Hz, 2H), 6.75 (t, J = 7.5 Hz, 1H), 7.14 (t, J =
13
6 C
.0 Hz, 4H), 7.64 (d, J = 8.1 Hz, 2H); C NMR (100 MHz, DMSO-d ): δ : 21.42, 50.13,
1
14.33, 117.93, 120.16, 127.09, 129.44, 129.90, 131.18, 139.42, 145.15. MS (m/z): 222.12
+
(
14 2
M ). Anal. calcd for C15H N : C, 81.08; H, 6.35; N, 12.59. Found: C, 65.20; H, 6.21; N, 12.43.
-
1
2
-(N-anilino)-2-(4-methoxy-phenyl)-acetonitrile (1e). M.p.: 94-96 °C. FTIR (KBr) (νmax, cm ):
-1 1
3
432, 2920, 2234, 1596, 1512, 1245, 1176, 822, 746, 680 cm . H NMR (400 MHz, DMSO-d ):
6
δ
H
: 3.82 (s, 3H), 3.94 (s, 1H), 5.32 (s, 1H), 6.74 (d, J = 8.7 Hz, 2H), 6.89 (t, J = 7.4 Hz, 1H),
13
6
.96 (d, J = 8.8 Hz, 2H), 7.22 (t, J = 7.2 Hz, 2H), 7.46 (d, J = 8.7 Hz, 2H); C NMR (100 MHz,
): δ : 49.78, 55.66, 114.14, 114.63, 118.40, 120.20, 126.12, 128.62, 129.58, 144.73,
60.43. MS (m/z): 238.11 (M ). Anal. calcd for C15
C, 75.34; H, 5.38; N, 11.56.
DMSO-d
1
6
C
+
14 2
H N O: C, 75.45; H, 5.58; N, 11.70. Found:
-
1
2
-(N-anilino)-2-(4-chlorophenyl) acetonitrile (1f). M.p.: 108-110 °C. FTIR (KBr) (νmax, cm ):
-1 1
3
316, 3026, 2950, 2239, 1606, 1458, 1263, 1240, 887, 758 cm . H NMR (400 MHz, DMSO-
d ): δ : 4.04 (bs, 1H), 5.42 (s, 1H), 6.74 (d, 2H, J = 7.6 Hz), 6.91 (t, 1H, J = 7.4 Hz), 7.26 (t, 2H,
6
H
13
6 C
J = 8.9 Hz), 7.48 (d, 2H, J = 8 Hz), 7.54 (d, 2H, J = 8 Hz); C NMR (100 MHz, DMSO-d ): δ :
1
2
64.73, 164.33, 142.26, 131.60, 129.76, 129.03, 126.88, 124.04, 121.16, 21.66. MS (m/z):
+
42.06 (M ). Anal. calcd for C14
H11ClN
2
: C, 69.28; H, 4.57; N, 11.54. Found: C, 69.11; H, 4.43;
N, 11.32.
-
1
2
-(4-Bromophenylamino)-2-phenylacetonitrile (1g). M.p.: 100-102 °C. FTIR (KBr) (νmax, cm ):
-1 1
3
6 H
325, 3038, 2963, 2235, 1599, 1228, 928, 762 cm . H NMR (100 MHz, DMSO-d ): δ : 3.98
(
sb, 1H), 5.32 (s, 1H), 6.64 (d, 2H, J = 8.3 Hz), 6.64 (t, 1H), 7.19 (t, 2H), 7.30 (d, 2H, J = 8.3
13
Hz), 7.52 (m, 2H). C NMR (400 MHz, DMSO-d
1
5
6
): δ
C
: 49.94, 113.42, 116.71, 119.81, 124.46,
+
28.62, 129.66, 132.37, 133.44, 143.38. MS (m/z): 286.01 (M ). Anal. calcd for C14H11BrN : C,
2
8.56; H, 3.86; N, 9.76. Found: C, 58.44; H, 3.56; N, 9.63.
ACKNOWLEDGEMENTS
Supports from the Payame Noor University in Isfahan Research Council and helps of Isfahan
University of Technology are gratefully acknowledged. The authors are also thankful to Mr. M.
Narimani, for providing useful chemicals.
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