Four-Component Synthesis of 2-Amino-3-Cyanopyridine Derivatives Catalyzed by Cu@imineZCMNPs as a Novel, Efficient and Simple Nanocatalyst Under Solvent-Free Conditions

Article abstract of DOI:10.1007/s10562-018-2318-3

Abstract: An efficient and convenient method was investigated for synthesis of 2-amino-3-cyanopyridine derivatives via a one-pot four-component reaction of various types of aldehydes, acetophenone, malononitrile, and ammonium acetate in the presence of 10

Full text of DOI:10.1007/s10562-018-2318-3

Catalysis Letters
https://doi.org/10.1007/s10562-018-2318-3
Four-Component Synthesis of 2-Amino-3-Cyanopyridine Derivatives
Catalyzed by Cu@imineZCMNPs as a Novel, Efficient and Simple
Nanocatalyst Under Solvent-Free Conditions
Asieh Yahyazadeh1 · Esmayeel Abbaspour‑Gilandeh1 · Mehraneh Aghaei‑Hashjin2
Received: 8 November 2017 / Accepted: 28 January 2018
© Springer Science+Business Media, LLC, part of Springer Nature 2018
Abstract
An efficient and convenient method was investigated for synthesis of 2-amino-3-cyanopyridine derivatives via a one-pot
four-component reaction of various types of aldehydes, acetophenone, malononitrile, and ammonium acetate in the presence
of 10 mg Cu@imineZCMNPs catalyst. The favorable products were achieved with high quantitative yields and easy isola-
tion of products in short reaction times under solvent-free conditions. The prepared catalytic system was characterized by
Fourier transform infrared spectroscopy, energy dispersive X-ray, thermogravimetric analysis, X-ray diffraction, transmission
electron microscopy, scanning electron microscopy and vibrating sample magnetometer. Due to the magnetic nature of the
catalyst, it can be easily recovered by an external magnetic field and comfortable reused.
Graphical Abstract
O
Ph
N
R
NH2
CN
Cu@imineZCMNPs
Solvent-free/80oC
RCHO
NH4OAC
NC
CN
Ph
Keywords Heterogeneous catalyst · 2-Amino-3-cyanopyridine · Solvent-free conditions · Reusable catalyst ·
Multicomponent reaction · Vibrating sample magnetometer
1 Introduction
separation methods through distillation or extraction, has
attracted high consideration in the synthetic chemistry, phar-
maceutical industry and technology fields and only negli-
gible changes in their selectivity and activity supplied the
possibility of their reuse [1–6].
The use of nanocatalysts in various organic reactions is an
interesting procedure to achieve green catalysis, which is
suitable for the environment and is of high interest in various
processes of chemical transformations which happened by
catalysis in heterogeneous conditions. During recent years,
the preparation of catalysts based on magnetic nanoparti-
cles, because of reasons such as the avoidance of tedious
The molecules containing pyridine moiety such as
2-amino-3-cyanopyridines has a wide pharmaceutical and
biological activities, such as IKK-β-inhibitors, A2A adeno-
sine receptor antagonists, antimicrobial, antiviral, antibac-
terial, antitumor, antifungal, antihypertensive, as well as
anti-inflammatory properties [7–14]. Numerous protocols
have been reported for the production of 2-amino-3-cyan-
opyridines that some of these procedures need long reac-
tion times, toxic solvent, high temperature, microwave or
ultrasound irradiation and multiple steps [15–19]. Hence, it
* Asieh Yahyazadeh
yahyazadeh@guilan.ac.ir
1
Chemistry Department, University of Guilan,
Rasht 41335-1914, Iran
2
Young Researchers and Elites Club, Ardabil Branch, Islamic
Azad University, Ardabil, Iran
Vol.:(0123456789)
1 3

A. Yahyazadeh et al.
Scheme 1 Cu@imineZCMNPs
catalyzed synthesis of 2-amino-
3-cyanopyridines
O
Ph
N
NH2
CN
Cu@imineZCMNPs
Solvent-free/80oC
RCHO
NH4OAC
NC
CN
Ph
R
Fig. 2 TGA curves of a MNPs and b Cu@imineZCMNPs
Fig. 1 FTIR spectra of ZCMNPs, AmpZCMNPs, imineZCMNPs and
Cu@imineZCMNPs
have been collectively assigned to the stretching vibration of
the C=C bond. Also, the presence of stretching vibrations
band in 1636 cm−1 is attributed to the imine C=N group.
It should be noted that the C=N signal of the Cu@imin-
eZCMNPs is shifted to a lower wavenumber than the C=N
stretching frequency of imineZCMNPs (1628 cm−1 rather
than 1636 cm−1). It is indicating that C=N bond is coordi-
nated to Cu metal through the lone pair of nitrogen.
is essential to expand an improved path for the synthesis of
2-amino-3-cyanopyridines under mild reaction conditions.
In continuation of our efforts to the synthesis of new cat-
alysts for organic transformations [20–24], we decided to
investigate the synthesis of 2-amino-3-cyanopyridine deriva-
tives with various substituents from the reaction of alde-
hyde, acetophenone, malononitrile and ammonium acetate
under solvent-free conditions using Cu@imineZCMNPs as
a novel, eco-friendly, reusable and promising nanocatalyst
(Scheme 1).
Thermogravimetric analysis (TGA) of MNPs and Cu@
imineZCMNPs was proved the presence of organic com-
pounds on the surface of magnetite nanoparticles (Fig. 2).
The TGA curve of MNPs demonstrates a weight loss of
approximately 5% up to a temperature of 430 °C, which
is concerned with the loss of the adsorbed water as well
as dehydration of the surface OH groups (Fig. 2a). TGA
of Cu@imineZCMNPs illustrates two considerable weight
loss steps due to the decomposition of the organic part of
aminopropyl and salicylaldehyde (Fig. 2b).
2 Results and Discussion
The infrared spectra of the ZCMNPs, AmpZCMNPs, imin-
eZCMNPs and Cu@imineZCMNPs samples in the region
of 400–4000 cm−1 are exhibited in Fig. 1. In the spectrum
of the ZCMNPs, the observed peak at 578 cm−1 correspond
to the Fe-O stretching frequency and a strong broadband
at 3435 cm−1 is related to the OH groups attached to the
iron. Appearance absorption band at 636 cm−1 in the spec-
tra is attributed to Zr-O groups, indicating magnetite nano-
particles functionalization has been done successfully. In
the spectrum of pure AmpZCMNPs, the observed peak at
1038 cm−1 is related to the stretching vibration of the Si-O
groups while the peaks appearing in the 2934 cm−1 region
can be attributed to the aliphatic C-H stretching vibration
mode. The 1419 and 1454 cm−1 bands in the imineZCMNPs
The XRD patterns of MNPs, imineZCMNPs and Cu@
imineZCMNPs represents diffraction peaks corresponding
to the cubic spinel phase of magnetic iron oxide nanopar-
ticles (JCPDS card No. 79-0417) and no peak dedicated to
Cu species appeared in the patterns of Cu@imineZCMNPs
compared those of imineZCMNPs, probably due to the tiny
size of Cu species (Fig. 3). This clearly illustrates that the
cubic spinel phase of imineZCMNPs remained intact upon
metal incorporation.
The surface morphology, size distribution and particle
shape of the Cu@imineZCMNPs were examined by scan-
ning electron microscopy (SEM) as shown in Fig. 4a. The
1 3

Four-Component Synthesis of 2-Amino-3-Cyanopyridine Derivatives Catalyzed by Cu@imineZCMNPs…
Fig. 5 TEM images of Cu@imineZCMNPs
Fig. 3 XRD patterns of MNPs, imineZCMNPs and Cu@imineZCM-
NPs
plasma atomic emission spectrometry (5.2% of Cu anchored
on catalyst).
SEM image of the Cu@imineZCMNPs clearly indicates
variations in the surface of these nanoparticles. The SEM
image shows that these nanoparticles are of nearly spheri-
cal morphology with mean diameter of about 48 nm. In the
case of recycled Cu@imineZCMNPs after the fifth cycle
of the reaction, the SEM image shown negligible change in
the size (56 nm) or morphology of the catalyst nanoparticles
(Fig. 4b).
The magnetic feature of the catalyst, which accounts for
its easy recovery, was surveyed with a vibrating sample mag-
netometer (VSM) at room temperature. Figure 7 shows the
magnetization diagram for the bare MNPs and Cu@imin-
eZCMNPs with the field sweeping from −8500 to +8500
Oersted. The saturation magnetization value of Cu@imin-
eZCMNPs nanoparticles emerged to be 39.86 emu/g, which
are much lower than the bare MNPs (61.22 emu/g) [25].
The TEM images of Cu@imineZCMNPs determined that
it appears to have an almost spherical shape with a narrow
size distribution (the average particle size is 30 nm, Fig. 5),
thereby retaining a nanocrystalline appearance. Therefore,
the great active sites of this nanocatalyst may allow for high
activity in organic transformations, even with a low catalyst
loading.
3 Screening of Reaction Conditions
In order to screen the reaction conditions for the synthesis
of 2-amino-4,6-diphenyl-nicotinonitrile (1a), a systematic
study considering different variables affecting the reaction
yield was investigated in a condensation reaction of benza-
ldehyde (1 mmol), acetophenone (1 mmol), malononitrile
(1 mmol), and ammonium acetate (1.5 mmol) as a model
reaction under solvent-free conditions. The results are listed
in Table 1. The initial optimization experiments revealed
that the desired product 1a was formed after 1 h in only 18%
Energy dispersive X-ray (EDX) mapping was performed
to verify the composition of the Cu@imineZCMNPs nano-
catalyst (Fig. 6). The EDX analysis illustrated the existence
of copper, iron, carbon, zirconium and silicon in the struc-
ture of Cu@imineZCMNPs catalyst that approved catalyst
preparation successfully. Also, the content of Cu in Cu@
imineZCMNPs was determined by Inductively coupled
Fig. 4 SEM images of Cu@
imineZCMNPs (a) and recycled
Cu@imineZCMNPs (b)
1 3

A. Yahyazadeh et al.
Fig. 6 EDX spectrum of
prepared Cu@imineZCMNPs
nanocatalyst
same amount of catalyst (10 mg) can also be greatly affected
in this transformation (entries 14–16). It is essential to men-
tion that the desired product could not be identified at room
temperature (entry 13). In addition, control experiments
demonstrated that any formation of the desired product 1a,
was obtained in the absence of the catalyst under solvent-
free conditions, even at 100 °C (entries 17 and 18).
After the successful generation of 1a, a variety of appro-
priate aldehydes (2a-q) were selected for the reaction aceto-
phenone, malononitrile and ammonium acetate in the pres-
ence of Cu@imineZCMNPs at 80 °C under solvent-free
condition, and desired 2-amino-3-cyanopyridine deriva-
tives were achieved in good to high yields without problems
which may be relevant to the use of solvents such as pollu-
tion, handling and safety. The optimized results are sum-
marized in Table 2. The electronic effect seemed to have
a clear influence on the reaction since aromatic aldehydes
with electron-donating groups (entries 12–15) illustrated rel-
atively low reactivity compared to the electron-withdrawing
and heteroaromatic groups (entries 2–11 and 16–17).
In a proposed mechanism, as depicted in Scheme 2. The
reaction may proceed via enamine 3, which generated from
the reaction of acetophenone and ammonium acetate, and
then activated by Cu2+ cation, reacts with alkylidenemalon-
onitrile 2 (generated from the reaction of aldehyde and malo-
nonitrle) to yield the corresponding intermediate 4, followed
by tautomerization and cycloaddition to give intermediate
6 which could isomerize and aromatize to afford the final
product.
Fig. 7 VSM magnetization curves of the bare MNPs and Cu@imin-
eZCMNPs
yield (entry 1). Moderate yields were obtained when the
same reaction was performed while utilizing DMF instead
of CHCl3 (entry 2). A closer examination illustrated that
when the DMF was replaced with acetone, the yield was
markedly improved (entry 3). Replacement of acetone with
ethyl acetate (entry 4) did not give an improved result, while
the formation of product 1a, was drastically increased when
using the same catalyst in acetonitrile at reflux condition
(entry 5). In contrast, utilizing EtOH and H2O, evidently
gave the desired product in lower yields (entries 6 and 7).
Surprisingly, highest yield (92%) was obtained when the
same reaction was carried out while utilizing a catalytic
amount (10 mg) of Cu@imineZCMNPs at 80 °C under
solvent-free conditions (entry 8). In the next phase of study,
the effect of catalyst loading on the completion of the reac-
tion was also investigated (entries 9–12). As shown, the best
result was obtained for 10 mg loading (entry 8). After further
survey, it was also observed that the use of heating with the
In the next phase of the study, the recovery and reuse
cycle of Cu@imineZCMNPs was also investigated. Hence,
we surveyed the recyclability of Cu@imineZCMNPs for
five consecutive cycles to afford the synthesis of 2-amino-
4,6-diphenyl-nicotinonitrile (1a). As shown in Fig. 8, this
nanocatalyst can be recycled at least five times with a negli-
gible decrease in the catalytic activity, and the yields ranged
from 92 to 87%.
1 3

Four-Component Synthesis of 2-Amino-3-Cyanopyridine Derivatives Catalyzed by Cu@imineZCMNPs…
Table 1 Optimization of the
reaction conditions in different
solvents
Entry
Solvent
Amount of
Temperature (°C)
Reaction time (h)
Yield (%)a
catalyst (mg)
1
2
3
4
5
6
7
8
CHCl3
DMF
Acetone
Ethyl acetate
Acetonitrile
EtOH
H2O
–
–
–
–
–
–
–
–
–
–
10
10
10
10
10
10
10
10
5
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
80
80
80
80
80
25
50
60
70
25
100
1
1
1
1
1
1
1
18
45
68
63
85
23
15
92
82
90
94
93
36
60
76
88
–
18 min
18 min
18 min
18 min
18 min
18 min
18 min
18 min
18 min
18 min
18 min
9
10
11
12
13
14
15
16
17
18
8
12
15
10
10
10
10
–
–
–
–
Reaction conditions: a mixture of benzaldehyde (1 mmol), acetophenone (1 mmol), malononitrile
(1 mmol), ammonium acetate (1.5 mmol) and Cu@imineZCMNPs (10 mg)
aIsolated yield
Table 2 Synthesis of 2-amino-
4,6-diphenylnicotinonitrile
derivatives in the presence of
the Cu@imineZCMNPs
Entry
Product
R
Yielda (%)
Time (min)
Mpb (°C) found
Mp (°C) (Lit)
1
2
3
4
5
6
7
8
1a
1b
1c
1d
1e
1f
1g
1h
1i
1j
1k
1l
1m
1n
1o
1p
1q
C6H5-
92
95
95
92
91
93
95
92
96
96
92
87
85
88
86
94
95
18
13
13
18
18
18
12
13
12
12
18
23
25
23
23
15
13
185–187
190–192
170–172
239–241
164–166
213–216
211–214
190–192
210–212
189–191
202–204
198–200
145–147
178–180
216–219
213–216
212–215
186–187 [26]
193–196 [27]
169–171 [28]
243–245 [28]
165–167 [28]
215–218 [29]
210–213 [28]
190–193 [28]
212–213 [26]
184–186 [30]
204–205 [31]
199–201 [28]
137–140 [28]
181–182 [26]
224–227 [28]
215–218 [29]
213–214 [31]
2-(Cl)-C6H4-
4-(Cl)-C6H4-
2,4-(Cl)2-C6H3-
3-(Br)-C6H4-
4-(Br)-C6H4-
4-(F)-C6H4-
3-(NO2)-C6H4
4-(NO2)-C6H4-
4-(CN)-C6H4-
4-(CO2Me)-C6H4-
2-(OCH3)-C6H4-
3-(OCH3)-C6H4-
4-(OCH3)-C6H4-
4-(CH3)-C6H4-
4-(pyridyl)-
9
10
11
12
13
14
15
16
17
3-(thiophene)-
Reaction conditions: aldehyde (1 mmol), acetophenone (1 mmol), malononitrile (1 mmol) and ammonium
acetate (1.5 mmol) and Cu@imineZCMNPs (10 mg), 80 °C
aIsolated yield
bMelting points are uncorrected
Furthermore, the catalytic efficiency and the capability
of Cu@imineZCMNPs with some of the other previously
explored methods were compared with those of other meth-
odologies which have been reported using other earlier
1 3

A. Yahyazadeh et al.
C
a
t
a
l
y
st
Cu
O
NH
HN
Cu2+
NH4OAC
-H2O
Ph
Ph
Ph
3
C
a
t
a
l
C
y
s
a
Cu
t
t
a
l
y
s
Cu
t
R
Ph
NH
N
O
NC
CN
-H2O/NH4OAC
H
R
NC
CN
2
H
CN
4
R
H
H
N
Ph
H
N
R
NH2
CN
Ph
NH2
N
Ph
H
NH
CN
(air)
O2
-H2
H
CN
6
5
R
R
Scheme 2 A proposed mechanistic pathway for the synthesis of 2-amino-3-cyanopyridines in presence of Cu@imineZCMNPs
homogeneous and heterogeneous catalysts for the synthesis
of 2-amino-4,6-diphenylnicotinonitrile derivatives (Table 3).
It is obvious that the reported protocol benefits from more
advantages such as the lack of need for using toxic solvents,
one step pathway and also low reaction time with high yields
under solvent-free conditions.
4 Conclusion
In conclusion, we have reported a simple, facile, and efficient
protocol the construction of a wide range of biologically and
pharmacologically active 2-amino-3-cyanopyridine in the
Fig. 8 Reusability of the catalyst
Table 3 Comparison the results
of the synthesis of 3,4-dihydro-
5-etoxycarbonyl-4-(4-phenyl)-
6-methylpyrimidine-2(1H)-one
using different catalysts
Entry
Catalyst and conditions
Reaction time (h)
Yield (%)b
Refs.
1
2
3
4
5
6
7
Nano Fe3O4/solvent-free/80 °C
Cellulose-SO3H /water/60 °C
Bu4N+Br−/water/reflux
Yb(PFO)/EtOH/reflux
FePO4/EtOH/reflux
Trifluoroethanol (TFE)/reflux
Cu@imineZCMNPs/solvent-free/80 °C
2
2.5
2
4
4
6
90
95
92
90
93
90
92
[26]
[32]
[33]
[34]
[35]
[36]
This work
18 min
1 3

Four-Component Synthesis of 2-Amino-3-Cyanopyridine Derivatives Catalyzed by Cu@imineZCMNPs…
presence of Cu@imineZCMNPs as a novel, environmen-
tally friendly and reusable heterogeneous catalyst via a direct
one-pot method starting from aldehydes, acetophenone,
malononitrile, and ammonium acetate under solvent-free
conditions.
help of ultrasonication for 1 h and then was stirred for 12 h.
After this period of time, the reaction mixture filtrated and
300 mL ethanol was added to filtrated solution to precipitate
core–shell Fe3O4@ZrO2 nanoparticles. Finally, the resulting
precipitate was dried under vacuum oven.
5.3 Functionalization of Fe3O4@ZrO2
with 3‑aminopropyltriethoxysilane
(AmpZCMNPs)
5 Experimental
All chemical materials were purchased from Merck chemical
company and used without further purification. The purity
determination of the product and reaction monitoring were
carried out using a TLC on silica gel PolyGram SILG/UV
254 plates. The melting points were measured with an Elec-
trothermal 9100 apparatus and are uncorrected. Fourier
transform infrared (FT-IR) spectra were recorded as KBr
pellets on a PerkinElmer PXI instrument. The broad angle
X-ray diffraction (XRD) measurements were accomplished
using Ni-filtered Co Ka radiation on a Siemens D-500
X-ray diffractometer (Germany) in the 2θ range of 10–80°.
Scanning electron micrographs (SEM) of the samples were
taken with SEM-LEO 1430VP. Thermogravimetric analysis
(TGA) was made on a Linseis SATPT 1000 thermoanalyzer
instrument. Samples were heated from 25 to 650 °C using a
rate of 10 °C min−1 under N2 atmosphere. Magnetic suscep-
tibility measurements were accomplished using a vibrating
sample magnetometer (VSM/AGFM, MDK Co, Ltd, Iran)
in the magnetic field range of − 8000 Oe to 8000 Oe at
room temperature. Inductively coupled plasma atomic emis-
sion spectrometry (ICP-AES) measurements were carried
out with VARIAN VISTA-MPX. Elemental analyses were
done on a Carlo-Erba EA1110CNNO-S analyzer and agreed
(within 0.30) with the calculated values.
Core–shell Fe3O4@ZrO2 nanoparticles (1 g) were dispersed
in dry toluene (20 mL) for 20 min using ultrasound and then
3-aminopropyltriethoxysilane (Amp, 2 mL) was added to the
resulting mixture. The mixture was refluxed for 24 h under
argon atmosphere. After 24 h, the functionalized magnetite
nanoparticles (MNP-AP) were separated from the reaction
mixture using a permanent magnet, washed several times
with ethanol and distilled water, and dried under vacuum
oven.
5.4 Functionalization of AmpZCMNPs
with Salicylaldehyde (imineZCMNPs)
To prepare imineZCMNPs, AmpZCMNPs (2 g) was dis-
persed in 20 mL of dry CH2Cl2 for 30 min. After that,
0.245 g of salicylaldehyde was added to the reaction mix-
ture and the mixture was refluxed for 6 h. Finally, these pre-
cipitates were separated by filtration, washed with 20 mL of
water, and then dried under vacuum oven.
5.5 Preparation of Cu@imineZCMNPs
Two grams of imineZCMNPs was suspended in 20 mL
of CH2Cl2. Thereafter, CuCl2 (0.25 mmol) was added to
CH2Cl2 (10 mL), and the reaction mixture was stirred for
24 h under argon atmosphere. After 24 h, the resultant pre-
cipitate formed was separated by filtration, and the product
was washed with water to remove unreacted metal precur-
sors. All stages of the Cu@imineZCMNPs synthesis are
shown in Scheme 3.
5.1 Preparation of Fe3O4 Nanoparticles (MNPs)
Fe3O4 MNPs were synthesized using traditional chemical
co-precipitation method. Typically, 2.36 g of FeCl3·6H2O
and 0.86 g of FeCl2·4H2O were dissolved in 40 mL distilled
water under stirring at 90 °C and continuous flow of argon
gas. Thereafter, under rapid mechanical stirring, 10 mL of
ammonia (25%) was added drop-wise to the reaction mix-
ture. The resulting black MNPs were magnetically separated
and washed the resulting black MNPs were magnetically
separated with deionized water and dried at 60 °C for 12 h.
5.6 Selected Spectral Data
5.6.1 2-Amino-4,6-Diphenylnicotinonitrile (1a)
1
Yield: 92%; White solid; m.p. 185–187 °C; H NMR
5.2 Preparation of Fe3O4@ZrO2 Nanoparticles
(ZCMNPs)
(400 MHz, CDCl3, ppm): δ 8.11 (s, 2H), 7.48 (m, 8H), 7.32
(s, 1H), 7.12 (s, 2H); 13CNMR (100 MHz CDCl3, ppm):
158.7, 155.2, 151.3, 138.9, 135.4, 127.6, 125.8, 123.1,
122.7, 121.9, 120.8, 119.7, 107.4, 84.5; FT-IR (KBr, cm−1):
3429, 3312, 3159, 2215, 1632, 1559, 1456, 1368, 1241, 751,
683. ESI-HRMS [M+H]+m/z Found: 271.1152. C18H13N3
Calculated: 271.1138.
Zirconium (IV) oxychloride octahydrate (ZrOCl2·8H2O)
(1 g) was dissolved in 50 mL of ethanol to form a clear solu-
tion and kept at 70 °C for 2 h. Then, Fe3O4 MNPs (5 g) was
added to that solution and the mixture was stirred with the
1 3

A. Yahyazadeh et al.
Scheme 3 Synthesis of Cu@imineZCMNPs
7. Murata T, Shimada M, Sakakibara S, Yoshino T, Kadono H,
Masuda T, Shimazaki M, Shintani T, Fuchikami K, Sakai K,
Inbe H, Takeshita K, Niki T, Umeda M, Bacon KB, Ziegelbauer
KB, Lowinger TB (2003) Bioorg Med Chem Lett 13:913
8. Hammam AG, EI-Hafez NAA, Midura WH, Mikolajczyk M,
Naturforsch Z (2000) B: J Chem Sci 55:417
5.6.2 2-Amino-4-(2-Chlorophenyl)-6-Phenylnicotinonitrile
(1b)
1
Yield: 95%; White solid; m.p. 190–192 °C; H NMR
(400 MHz, CDCl3, ppm): δ 8.05 (s, 2H), 7.45 (s, 4H), 7.32
(s, 1H), 7.16 (s, 2H), 7.07 (s, 1H), 6.89 (s, 2H); 13CNMR
(100 MHz CDCl3, ppm): 158.3, 155.2, 154.1, 152.5, 135.4,
129.8, 129.7, 127.4, 126.9, 125.2, 124.7, 119.4, 115.2,
111.4, 109.7, 84.3, 56.11; FT-IR (KBr, cm−1): 3435, 3327,
2221, 1634, 1543, 1439, 1368, 1241, 751, 683. ESI-HRMS
[M + H]+m/z Found: 305.0707. C18H12ClN3 Calculated:
305.0756.
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(1h)
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1
Yield: 92%; Yellow solid; m.p. 190–192 °C; H NMR
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(400 MHz, CDCl3, ppm): δ 8.18 (s, 2H), 7.49 (s, 4H),
7.27–7.34 (m, 3H), 7.06–7.16 (m, 3H); 13CNMR
(100 MHz CDCl3, ppm): 161.2, 160.1, 159.4, 155.2,
139.4, 136.8, 130.4, 128.2, 127.3, 126.4, 119.3, 118.1,
116.9, 111.7, 107.4, 83.1, 54.2; FT-IR (KBr, cm−1): 3432,
3310, 3162, 2200, 1627, 1549, 1535, 1248, 860, 755, 685.
ESI-HRMS [M + H]+m/z Found: 317.2148. C18H12N4O2
Calculated: 316.1089.
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Acknowledgements We gratefully acknowledge financial support of
this work by the Research Council of the University of Guilan.
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