Synthesis of a novel acidic ionic liquid catalyst and its application for preparation of pyridines via a cooperative vinylogous anomeric-based oxidation

Article abstract of DOI:10.1007/s11164-020-04361-y

Abstract: In the current study, a novel acidic ionic liquid catalyst based on 8-hydroxyquinoline, namely 8,8′,8″-([1,3,5-triazine-2,4,6-triyl]tris[oxy])tris(1-sulfoquinolin-1-ium)chloride (TTS), was designed and synthesized. The structure of the prepared acidic ionic liquid (AIL) was fully investigated by using Fourier transform infrared (FT-IR) spectroscopy, energy dispersive X-ray (EDX) analysis, thermogravimetric analysis/differential thermal analysis (TGA/DTA), ¹HNMR, ¹³CNMR and mass spectroscopy. Then, the catalytic performance of described AIL was successfully inspected toward the four-component synthesis of pyridine derivatives via a cooperative vinylogous anomeric-based oxidation. Graphic abstract: Novel AIL (TTS) showed a very high efficiency in the synthesis of pyridines. [Figure not available: see fulltext.].

Full text of DOI:10.1007/s11164-020-04361-y

Research on Chemical Intermediates (2021) 47:1643–1661
https://doi.org/10.1007/s11164-020-04361-y
Synthesis of a novel acidic ionic liquid catalyst and its
application for preparation of pyridines via a cooperative
vinylogous anomeric‑based oxidation
Mohammad Rahmati1 · Davood Habibi1
Received: 17 September 2020 / Accepted: 11 December 2020 / Published online: 12 January 2021
© The Author(s), under exclusive licence to Springer Nature B.V. part of Springer Nature 2021
Abstract
In the current study, a novel acidic ionic liquid catalyst based on 8-hydroxyquino-
line, namely 8,8′,8″-([1,3,5-triazine-2,4,6-triyl]tris[oxy])tris(1-sulfoquinolin-1-ium)
chloride (TTS), was designed and synthesized. The structure of the prepared acidic
ionic liquid (AIL) was fully investigated by using Fourier transform infrared (FT-IR)
spectroscopy, energy dispersive X-ray (EDX) analysis, thermogravimetric analysis/
1
diferential thermal analysis (TGA/DTA), HNMR, 13CNMR and mass spectros-
copy. Then, the catalytic performance of described AIL was successfully inspected
toward the four-component synthesis of pyridine derivatives via a cooperative viny-
logous anomeric-based oxidation.
Supplementary Information The online version of this article (https://doi.org/10.1007/s11164-020-
04361-y) contains supplementary material, which is available to authorized users.
* Davood Habibi
davood.habibi@gmail.com
1
Department of Organic Chemistry, Faculty of Chemistry, Bu-Ali Sina University,
6517838683 Hamedan, Iran
Vol.:(0123456789)
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M. Rahmati, D. Habibi
Graphic abstract
Novel AIL (TTS) showed a very high efciency in the synthesis of pyridines.
Keywords Acidic ionic liquid · Anomeric-based oxidation · Cooperative vinylogous
anomeric-based oxidation · Ionic liquid · Pyridine
Introduction
Ionic liquids (ILs) are composed entirely of ions, and their high steric hindrances
cause the ions to bond poorly to each other, resulting in their melting point below
100 °C or even at room temperature [1]. These compounds have distinctive prop-
erties that in addition to low melting point, include high polarity, extremely low
vapor pressure, low fammability, high temperature range in the liquid state, easy
recyclability, adjustable mixability with water and other solvents, conductivity and
thermal, chemical and electrochemical stability [2]. In addition, the physicochemical
properties of these compounds can be adjusted by changing the cation structure and
the cation–anion combination [3]. Due to the mentioned properties, in recent years,
much attention has been paid to these compounds and have found many applications
in various felds such as pharmacy [4], nanomaterials [5], and catalytic chemistry [6,
7]. Based on the properties, ILs can be classifed into three categories: acidic, alka-
line and neutral. An AIL can be defned as a low melting ionic salt with acidic char-
acteristics [8]. The use of AILs in biomass processes has received a great deal of
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Synthesis of a novel acidic ionic liquid catalyst and its…
1645
attention in the last ten years [9, 10]. AILs have been used extensively as catalysts in
esterifcation [11], alkylation [12–16], acetylation [17], heterocyclic synthesis reac-
tions [18], dehydration [19], oxidation [20] and polymerization [21] reactions.
The design and application of high-efciency catalysts in the synthesis of organic
materials has attracted much attention [22]. Organocatalysts had special superiority
in the production of pharmaceutical materials compared to (transition) metal cat-
alysts. In addition, organocatalysts are not usually expensive, are stable, are easy
to get accessible, have low toxicity and are not sensitive to moisture and oxygen
[23–35]. Despite their controversy as greener compounds, ILs can be considered as
organocatalysts [36].
The preference of the axial position for an electron acceptor group (electronega-
tive atom) adjacent to an electron donor group (lone pairs) over the equatorial posi-
tion is an important stereoelectronic phenomenon called the anomeric efect [37–45]
(Scheme 1).
Scientists have proposed hypotheses for the superiority of the axial position [46].
Figure 1 shows the most frequently considered explanations for these hypotheses
in the case of tetrahydropyrans. According to Edward, the reason for the superior-
ity of the axial position over the equatorial position is the less repulsion between
polar interactions in the axial position than the equatorial position (Fig. 1a) [47].
Of course, according to Lemiux and Chou, electrostatic dipolar interactions can be
considered as coulombic interactions if the bond moments responsible for Edward’s
Scheme 1 Axial preference for
acceptor group at the anomeric
position
(a)
(b)
(d)
(c)
Fig. 1 Most frequently considered explanations hypotheses have been proposed to account for the ano-
meric efect in substituted tetrahydropyran [57]
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M. Rahmati, D. Habibi
dipolar repulsions are considered as point charges located at the center of each atom
(Fig. 1b) [48–50]. More recently, the idea has been suggested by Takahashi, Coheno
and Nishio that a non-classical hydrogen bond exists between the axial X group
at carbon-1 and the syn-axial hydrogen attached to carbon-5 (Fig. 1c) [51–53]. In
this phenomenon (anomeric efect), which is a kind of negative hyperconjugation,
the electron density is delocalized from lone-pair orbital to the empty anti-bonding
sigma orbital (n→σ*) (Fig. 1d) [54–56].
An interesting example of the role of the anomeric efect in the nature is the con-
version of α-D-glucopyranose to ß-D-glucopyranose (Scheme 2).
Vinylogous anomeric efect (VAE) is one of the subsets of anomeric efect
[58–66]. The VAE occurred when the anomeric efect extended through double
bonds. Scheme 3 represents the general modes of anomeric efect and VAE [67].
According to a study by Katritzky, the facile dissociation of the C–N bond of
benzotriazole residue in compound A is related to the VAE (Scheme 4) [60].
On the other hand, pyridines are excellent compounds that are used in various
felds such as pharmacy, agricultural chemicals, materials science. The biological
importance of these compounds is clearly known as anti-tumor [69], anti-fungal
[70], anti-virial [71] and anti-tuber- culosis [72]. In nature, important compounds
such as nicotinic acid (vitamin B3) and pyridoxine (vitamin B6) and many medici-
nal compounds contain pyridine in their structures (Fig. 2).
Scheme 2 Conversion of
α-D-glucopyranose to ß-D-
glucopyranose
α-D- glucopyranose
ß-D- glucopyranose
Scheme 3 Anomeric efect versus VAE
H
H
Bt
H
Bt
d-
Bt
Bt = Benzotriazole
O
O
A
O
d+
Scheme 4 VAE causes facile C–N bond dissociation of the benzotriazole residue [68]
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Synthesis of a novel acidic ionic liquid catalyst and its…
1647
Nicotinic acid
(vitamin B3)
Pyridoxine
(vitamin B6)
Omeprazole
(Stomach acid lowering)
Topoisomerase
inhibitor
(Anti-cancer)
Fig. 2 Structure of some important pyridine derivatives
Over the years, various methods have been developed to synthesize pyridines as
valuable compounds [73–82]. Many of these methods are not efcient in terms of
efciency, reaction time, and reaction conditions. Therefore, proposing new meth-
ods for synthesizing these compounds that have high efciency and are greener is
the aspiration of many. In this paper, to realize this dream and also to present a new
and efective method for the synthesis of valuable biological structures using AIL
catalysts, we reported the rational design, synthesis, identifcation and catalytic per-
formance of a new AIL based on 8-hydroxy quinoline called TTS in the synthesis of
pyridines via a cooperative vinylogous anomeric-based oxidation. (Schemes 5 and
6).
Experimental
Chemicals were purchased from the Fluka and Merck chemical companies and
used without further purifcation. The reaction progress and purity of the prepared
structures were monitored by TLC (silica gel SIL G/UV 254) plates. The FT-IR
spectra were recorded on a PerkinElmer Spectrum Version 10.02.00 using KBr
1
pellets. The HNMR (300) and 13CNMR (75) spectra were recorded on a Bruker
spectrometer (δ in ppm) using DMSO-d6 as solvent with chemical shifts measured
relative to Si(CH3)4 as an internal standard. Melting points were determined with
a Buchi B-545 melting point apparatus in open capillary tubes. Mass spectra were
recorded on an AB SCIEX 3200 QTRAP apparatus. Thermogravimetric analyses
Scheme 5 General route toward the synthesis of TTS
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M. Rahmati, D. Habibi
Scheme 6 Synthesis of pyridines using TTS as catalyst
were carried out using a Rheometric Scientifc STA 1500 TGA apparatus. Elemental
mapping analysis and EDS were carried out using a FESEM device model SIGMA
VP company ZEISS Germany equipped with detector EDS-mapping-WDS and
FBSD company oxford instruments UK.
General procedure for preparation of TTS
Cyanuric chloride (1.84 g, 10 mmol) in dioxane (50 mL) was added slowly to a solu-
tion of 8-hydroxyquinolone (4.78 g, 33 mmol) and dioxane (50 mL) in 0 °C and then
anhydrous K2CO3 (10 g, 70 mmol) was added to resulting solution and was refuxed
for 24 h in 80 °C with stirring. The reaction mixture was cooled to room tempera-
ture then poured onto flter paper. The almost yellow precipitate that remained on
the flter paper was washed several times with distilled water until the precipitate
turned white and then washed with ethanol. The resulting precipitate was placed
in an oven at 100 °C for 2 h until completely dry. The melting point of the prod-
uct (2,4,6-Tris[quinolin-8-yloxy]-1,3,5-triazine) which previously reported [83] was
286 °C. In the following, 1.2 mL of chlorosulfonic acid with a density of 1.75 g/mL
(18 mmol) was dissolved in 50 cc of dioxane, then by stirring this solution, 2.6 g of
the (2,4,6-tris[quinolin-8-yloxy]-1,3,5-triazine) at 0 °C was added to it. After one
1 3

Synthesis of a novel acidic ionic liquid catalyst and its…
1649
hour, the yellow precipitate obtained, which was the new ionic liquid, was removed
from the solution and purifed with dichloromethane. The general outline of this
reaction is shown in the Scheme 5.
General procedure for preparation of pyridine derivatives using TTS
A mixture of ketone derivatives (1 mmol), aldehydes (1 mmol), ammonium acetate
(77 mg, 1 mmol, as a precursor for in-situ generation of ammonia), malononitrile
(66 mg, 1 mmol) or ethylcyanoacetate (113 mg, 1mmole) and AIL (40 mg) in a
10-mL round-bottomed fask was stirred in an oil-bath at 80 °C. After reaction com-
pletion, as monitored by TLC, to separate AIL and other impurities, crude products
washed several times with water and warm ethanol. The remaining solid (pure prod-
uct) was dried in oven.
Results and discussion
The formation of TTS was verifed with several skills including FT-IR, EDX, TGA/
DTA and elemental mapping are discussed in more detail below.
The IR spectrum of the TTS showed a wide peak in the range 2850–3300 cm−1,
which is related to the O–H stretching of SO3H. The two peaks observed at
1060 cm−1 and 1175 cm−1 correspond to vibrational modes of N–SO2 and O–SO2
bonds. Another peak in 1011 cm−1 could be related to the S=O bond (Fig. 3).
By using EDX analysis, the elemental composition of the prepared TTS was
explored. As predicted, carbon, oxygen, chlorine, sulfur, and nitrogen were detected
in the EDX results (Fig. 4). Therefore, according to the EDX results, the structure of
the novel-synthesized AIL is completely inferred.
The thermal behavior of the catalyst was also evaluated using TGA/DTA analy-
sis. The obtained data from this analysis is shown as a plot (Fig. 5). The weight loss
up to 175 °C is related to the evaporation of solvents used during the preparation of
TTS. Between 300 and 360 °C, about 28% weight loss occurs, which is due to the
decomposition of the catalyst acidic groups. Another major weight loss up to 450 °C
is related to the decomposition of compound and breaking of C–O bonds. And at
higher temperatures, its bonds decompose and a small percentage of it remains.
These results indicated the high thermal stability of the TTS.
Fig. 3 FT-IR spectrum of TTS
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M. Rahmati, D. Habibi
Fig. 4 EDX analysis of TTS
Fig. 5 TGA/DTA plot of TTS
Examination of the elemental mapping analysis showed the presence of C, Cl, O,
N and S elements in the catalyst with a good ratio over the catalyst surface (Fig. 6).
After characterization of TTS as a new AIL, we investigated its catalytic per-
formance for the synthesis of pyridines via vinylogous anomeric-based oxidation.
To achieve this goal, we initially performed a model reaction with the reaction of
4-chlorobenzaldehyde, 4-chloroacetophenone, malononitrile and ammonium ace-
tate as a source of nitrogen production (raw materials of production 1a) in order to
fnd the best reaction conditions. To fnd the best results in terms of yield and reac-
tion time, we scrutinized the role of efective parameters such as solvents, reaction
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Synthesis of a novel acidic ionic liquid catalyst and its…
1651
Fig. 6 Elemental mapping images of oxygen (red), nitrogen (green), sulfur (violet), chlorine (gray), car-
bon (pale green) of TTS. (Color fgure online)
temperature, and amount of catalyst to the selected model to produce the desired
product (Table 1). The obtained data are summarized in Table 1. The achieved data
showed that the best results were obtained when 40 mg of TTS was used at 80 °C
(Table 1, entry 4). The reaction was also performed in the absence of catalyst, but no
product was formed (Table 1, entry 5).
Next, knowing the optimal reaction conditions, we focused on diferent substrates
for the preparation of pyridine derivatives which the results are given in Table 2.
The data show that the desired molecules were obtained in a short reaction time with
high efciency. All synthesized pyridine derivatives were identifed by melting point
measurements and spectroscopic techniques such as FT-IR, 1HNMR and 13CNMR.
A reasonable mechanism for the synthesis of desired molecule (1 g) is showed
in Scheme 7. Initially, TTS as a catalyst activates the aromatic carbonyl ketone
group which reacts with ammonia and produces intermediate 2 and is converted
to 3 after tautomerization. The reaction will continue with the nucleophilic attack
of the produced enamine 3 to the Knoevenagel product 4. In the presence of the
TTS, this reaction leads to intermediate 5 and after tautomerization to intermediate
6 which is converted through an intramolecular nucleophilic attack to intermediate
7. In the next step, after tautomerization, intermediate 7 is converted to intermedi-
ate 8. According to the recent introduced term entitled “anomeric-based oxidation”
(ABO) [68, 84–91], intermediate 8, both endocyclic and exocyclic nitrogen atoms
assist hydride departure and releasing of molecular hydrogen (H2). For approving
the above-mentioned idea, the model reaction was performed in the absence of any
molecular oxygen, both under argon and nitrogen atmosphere. The obtained data for
model reaction under air, argon and nitrogen atmosphere are similar (Table 1, entry
4). (Finally, deprotonation of intermediate 9 generates the desired molecule 1 g.
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M. Rahmati, D. Habibi
Table 1 Optimization of reaction conditions for synthesis of pyridine derivativesa
Entry
Solvent
Temperature
(°C)
Catalyst loading Time (min.)
(mg)
Yield (%)b
1
2
–
–
–
–
–
–
–
25
40
70
80
80
80
80
80
80
80
80
80
40
40
40
40
–
20
60
40
40
40
40
40
60
60
25
15
60
15
15
60
60
60
60
60
trace
25
50
3
4c
5
80
trace
trace
80
trace
30
trace
30
trace
6
7
8
9
10
11
12
H2O
C2H5OH
Ethyl acetate
n-hexane
CHCl3
aReaction conditions: 4-Chlorobenzaldehyde (140.5 mg, 1 mmol), malononitrile (66 mg, 1 mmol),
4-chloroacetophenone (154.5 mg, 1 mmol) and ammonium acetate (77 mg, 1 mmol)
bIsolated yields
cData for the model reaction under air, argon and nitrogen are similar
According to Table 3, the method used in this paper for the synthesis of pyri-
dines is superior to many previously reported methods in terms of reaction ef-
ciency, short reaction time, no need for solvent and ease of reaction.
Conclusion
In this work, TTS as an acidic catalyst was designed, synthesized, and identi-
fed by several skills including FT-IR, EDX, elemental mapping, TGA/DTA,
1HNMR, 13CNMR and mass spectroscopy. Then, the compound is used to make
pyridine derivatives in a four-component reaction. The main advantages of this
method include low cost, high efciency, short reaction time, ease of method
and no need for solvent.
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Synthesis of a novel acidic ionic liquid catalyst and its…
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Table 2 Synthesis of pyridine derivatives in the presence of TTS
[92]
[94]
[93]
[93]
[93]
[95]
[92]
[96]
[92]
[96]
[92]
[97]
[92]
[98]
[98]
[99]
[98]
[98]
[100]
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M. Rahmati, D. Habibi
Scheme 7 A reasonable mechanism for the synthesis of desired molecule (1 g) in the presence of TTS
Table 3 Comparison study of prepared catalyst with some other reported catalysts
(1) [Bmim][BF4], Solvent free, 60 °C, 5 h, 88% [76]
(2) Ethyl ammonium nitrate, Solvent free, Refux, 60 °C, 2.5 h, 90% [77]
(3) Fe3O4@TiO2@O2PO2(CH2)NHSO3H, Solvent free, 90 °C, 25 min, 87% [92]
(4) Cellulose-SO3H, H2O, 60 °C, 2.5 h, 94% [93]
(5) TTS, Solvent free, 80 °C, 15 min, 85%, [current work]
(1) [Bmim][BF4], Solvent free, 60 °C, 5 h, 78% [76]
(2) Ethyl ammonium nitrate, Solvent free, Refux, 60 °C, 2 h 88%, [77]
(3) NMS(5 mol%), Solvent free, 80 °C, 40 min, 91%, [79]
(5) Bu4N+ Br−(10 mol%), H2O, Refux, 2 h, 73%, [80]
(6) TTS, Solvent free, 80 °C, 20 min, 80%, [current work]
(1) ClO4−/Al-MCM-41, Solvent free, 100 °C, 30 min, 79% [81]
(2) NMS(5 mol%), Solvent free, 80 °C, 50 min, 85%, [79]
(3) Cellulose-SO3H, H2O, 60 °C, 3 h, 90% [93]
(4) TTS, Solvent free, 80 °C, 17 min, 80%, [current work]
(1) Bu4N+ Br−(10 mol%), H2O, Refux, 2 h, 92%, [80]
(2) Fe3O4@TiO2@O2PO2(CH2)NHSO3H, Solvent free, 90 °C, 20 min, 90% [92]
(3) [BBIM]Br, Solvent free, 28 °C, 5 h, 78%, [82]
(4) [BBIM]BF4, Solvent free, 28 °C, 4.5 h, 81%, [82]
(5) Cellulose-SO3H, H2O, 60 °C, 2.5 h, 95%, [93]
(6) TTS, Solvent free, 80 °C, 17 min, 80%, [current work]
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Synthesis of a novel acidic ionic liquid catalyst and its…
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Selected spectral data
M.p. 286 °C. FT-IR (KBr, ν, cm−1): 3068.5, 1579.12, 1554.95, 1529.86, 1499.83,
1
1469.92, 1362.71, 1239.89, 1292.71, 1165.66, 115.32, 944.48, 792.62, 755.05. H
NMR (300 MHz, DMSO-d6) δ 8.83(d, J=3 Hz, 3H), 8.44–8.32 (m, 3H), 7.96–7.92
(m, 3H), 7.85–7.47 (m, 9H), 13C NMR (75 MHz, DMSO-d6) δ 174.13, 151.02,
147.54, 140.45, 136.54, 129.46, 126.76, 126.66, 122.62, 121.45.
M.p. 91–93 °C. FT-IR (KBr, ν, cm−1): 3051, 1727, 1600, 1557, 1359, 1175, 1060,
1
1011, 582, H NMR (300 MHz, DMSO-d6) δ 11.19 (s, 3H, SO3H), 9.15 (dd,
J=20 Hz, J=6 Hz, 6H), 8.10 (dd, J=9 Hz, J=6 Hz, 3H), 7.79 (d, J=3 Hz, 6H),
7.50 (t, J=3 Hz, 3H), 13C NMR (75 MHz, DMSO-d6) δ 150.41, 148.70, 147.02,
144.80, 130.99, 130.23, 129.09, 122.92, 119.04, 116.53, MS: ESI-mass: m/z=860.
M.p. 255 °C. FT-IR (KBr, ν, cm−1): 3503, 3395.28, 2205.84, 1609.11, 1581,
1
1545.87, 1493.83, 1093.69, 1013, 823.05. H NMR (300 MHz, DMSO-d6) δ 8.17
(d, J=6 Hz, 2H), 7.72 (d, J=6 Hz, 2H), 7.64 (d, J=9 Hz, 2H), 7.57 (d, J=9 Hz,
2H), 7.32 (s, 1H), 7.13 (bs, 2H, NH2), 13C NMR (75 MHz, DMSO-d6) δ 161.24,
1 3

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M. Rahmati, D. Habibi
157.88, 154.19, 136.66, 136.06, 135.51, 135.07, 130.70, 129.45, 117.27, 109.53,
87.29.
M.p. 230 °C. 1H NMR (300 MHz, DMSO-d6) δ 9.97 (s, 1H, OH), 8.03 (d, J=9 Hz,
2H), 7.78 (d, J=9 Hz, 2H), 7.64 (d, J=9 Hz, 2H), 7.19 (s, 1H), 6.96 (s, 2H, NH2),
6.88 (d, J=9 Hz, 2H), 13C NMR (75 MHz, DMSO-d6) δ 161.25, 160.12, 159.28,
153.75, 136.85, 132.14, 130.95, 129.48, 128.72, 123.55, 117.64, 115.90, 108.50,
85.47.
M.p. 255 °C. FT‐IR (KBr, ν, cm−1): 3497.6, 3463.2, 3354.64, 2207.95, 1566.47,
1
1547.38, 1231.97, 1093.97, 819.86, 617.95. H NMR (300 MHz, DMSO-d6) δ
9.98 (s, 1H, OH), 8.03 (d, J=9 Hz, 2H), 7.71 (d, J=9 Hz, 2H), 7.64 (d, J=9 Hz,
2H), 7.19 (s, 1H), 6.95 (bs, 2H, NH2), 6.88 (d, J=9 Hz, 2H), 13C NMR (75 MHz,
DMSO-d6) δ 161.23, 160.10, 159.26, 153.71, 136.48, 134.85, 130.71, 129.48,
129.22, 128.72, 117.64, 115.90, 108.57, 85.55.
M.p. 215 °C. FT-IR (KBr, ν, cm−1): 3471.8, 3276.6, 3144.95, 2214.4, 1627.67,
1
1556.21, 1492.12, 1090.74, 698.32. H NMR (300 MHz, DMSO-d6) δ 7.62 (d,
J=9 Hz, 2H), 7.50–7.44 (m, 7H), 6.82 (bs, 2H, NH2), 1.83 (s, 3H, CH3), 13C NMR
(75 MHz, DMSO-d6) δ 162.05, 158.50, 154.48, 140.33, 136.38, 134.08, 130.86,
129.23, 128.90, 128.43, 116.98, 89.41, 17.17.
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Synthesis of a novel acidic ionic liquid catalyst and its…
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M.p>300 °C. FT‐IR (KBr, ν, cm−1): 3468.9, 3288, 3154.06, 2214.4, 1632.55,
1
1556.77, 1438.37, 1102.39, 769.23, 702.47, 616.21. H NMR (300 MHz, DMSO-
d6) δ 8.70 (d, J=6 Hz, 1H), 8.63 (s, 1H), 7.91 (d, J=6 Hz, 1H,), 7.61–7.58 (m,
1H), 7.57–7.45 (m, 5H), 6.87 (bs, 2H, NH2), 1.85 (s, 3H, CH3), 13C NMR (75 MHz,
DMSO-d6) δ 162.19, 158.56, 152.26, 150.32, 149.18, 140.23, 136.81, 133.49,
129.25, 128.97, 128.46, 124.10, 117.45, 116.94, 89.59, 17.20.
M.p. 201 °C. FT-IR (KBr, ν, cm−1): 3477.5, 3291, 3139.5, 2211.37, 1633.49,
1557.66, 1371.6, 1097.76, 773.19, 707.8, 615.15. 1H NMR (300 MHz, DMSO-d6) δ
7.52–7.43 (m, 5H), 7.34 (d, J=6 Hz, 2H),7.27 (d, J=6 Hz, 2H), 6.72 (bs, 2H, NH2),
2.38 (s, 3H, CH3), 1.82 (s, 3H, CH3), 13C NMR (75 MHz, DMSO-d6) δ 161.86,
158.53, 155.81, 150.42, 144.51, 140.47, 138.61, 134.59, 130.02, 129.68, 129.22,
128.83, 128.73, 128.41, 117.19, 89.75, 21.34, 17.22.
M.p. 170–180 °C. FT-IR (KBr, ν, cm−1): 3471.8, 3146.12, 2212.00, 1625.96,
1555.12, 1489.65, 1439.63, 1247.49, 1070.98, 1007.31, 826.99, 769.92, 697.94,
1
615.49, H NMR (300 MHz, DMSO-d6) δ 7.75 (d, J=6 Hz, 2H), 7.52–7.43 (m,
5H), 7.39 (d, J=9 Hz, 2H), 6.82 (bs, 2H, NH2), 1.83 (s, 3H, CH3), 13C NMR
(75 MHz, DMSO-d6) δ 162.08, 158.54, 154.48, 150.56, 140.31, 136.73, 132.17,
131.08, 129.23, 128.89, 128.42, 122.78, 117.08, 117.01, 89.37, 17.17.
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M. Rahmati, D. Habibi
M.p>300 °C. FT-IR (KBr, ν, cm−1): 3021, 2843, 2214.4, 1630.97, 1493.02,
1
1225.50, 1091.08, 1013.29, 819.26, 563.33. H NMR (300 MHz, DMSO-d6) δ
10.29 (bs, 1H, OH), 7.96 (d, J=9 Hz, 2H), 7.77 (d, J=9 Hz, 2H), 7.65 (d, J=9 Hz,
2H), 7.60 (d, J=9 Hz, 2H), 6.90 (s, 1H). 13C NMR (75 MHz, DMSO-d6) δ 162.65,
158.66, 151.29, 136.55, 135.83, 135.19, 131.85, 130.69, 130.09, 129.37, 129.31,
116.75, 107.12, 98.72.
M.p. 233–235 °C. FT-IR (KBr, ν, cm−1): 3422.55, 3149.15, 2927.36, 2214.15,
1646.76, 1555.24, 1420.68, 1253.24, 1095.21, 756.77, 703.67, 614.65.1H NMR
(300 MHz, DMSO-d6) δ 7.50–7.44 (m, 3H), 7.29 (d, J=6 Hz, 2H), 6.58 (bs, 2H,
NH2), 2.70 (t, J=6 Hz, 2H, CH2), 2.19 (t, J=6 Hz, 2H, CH2), 1.73–1.71 (m, 2H,
CH2), 1.60–1.58 (m, 2H, CH2), 13C NMR (75 MHz, DMSO-d6) δ 161.43, 158.38,
154.42, 136.85, 129.05, 128.99, 128.52, 118.79, 117.14, 88.52, 33.29, 26.33, 22.92,
22.57.
Acknowledgements We thank the Bu-Ali Sina University, Hamedan Iran for the support of this project.
Also, we thank Dr. Meysam Yarie and Mr Morteza Torabi for their helps in the course of this research.
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