Introduction of a new bis-derivative of succinimide (Bis-Su) as a sustainable and efficient basic organo-catalyst for the synthesis of arylidene malononitrile and tetrahydrobenzo[b]pyran derivatives under green conditions

Article abstract of DOI:10.1007/s11164-020-04235-3

Organo-catalysts have been under great consideration for many years because of their performance and selectivity in the reactions. In this work, a new bis-succinimide (Bis-Su) compound is prepared, identified and used as a green and efficient basic organo

Full text of DOI:10.1007/s11164-020-04235-3

Research on Chemical Intermediates
https://doi.org/10.1007/s11164-020-04235-3
Introduction of a new bis‑derivative of succinimide
(
Bis‑Su) as a sustainable and eꢀcient basic organo‑catalyst
for the synthesis of arylidene malononitrile
and tetrahydrobenzo[b]pyran derivatives under green
conditions
1
1
1,2
Fariba Hassanzadeh · Nader Daneshvar · Farhad Shirini
Manouchehr Mamaghani1
·
,2
Received: 11 April 2020 / Accepted: 6 August 2020
©
Springer Nature B.V. 2020
Abstract
Organo-catalysts have been under great consideration for many years because of
their performance and selectivity in the reactions. In this work, a new bis-succin-
imide (Bis-Su) compound is prepared, identiꢀed and used as a green and eꢁcient
basic organo-catalyst for the promotion of the synthesis of arylidene malononitrile
and tetrahydrobenzo[b]pyran derivatives. Using this method, both of the reactions
were performed under mild conditions, during short reaction times in high yields.
The catalyst can also be recycled and reused several times without a considerable
decrease in its activity.
Keywords Organo-catalyst · Bis-succinimide · Arylidene malononitriles ·
Tetrahydrobenzo[b]pyran · Water media
Electronic supplementary material The online version of this article (https://doi.org/10.1007/s1116
4
-020-04235-3) contains supplementary material, which is available to authorized users.
*
Farhad Shirini
shirini@guilan.ac.ir
Nader Daneshvar
ndxdaneshvar@gmail.com
1
2
Department of Chemistry, College of Science, University of Guilan, University Campus 2,
Rasht, Iran
Department of Chemistry, College of Sciences, University of Guilan, Rasht, Iran
Vol.:(012
1
3456789)
3

F. Hassanzadeh et al.
Introduction
In recent years, the use of green and commercially available or easily preparable
catalysts in organic reactions has been under attention because they do not contami-
nate the environment and are economically aꢂordable. In this way, organo-catalysts
as compounds that have the only hydrogen, carbon, nitrogen, sulfur and phosphor
atoms in their structure have been extensively followed up since they are usually,
inexpensive, easily available, non-toxic and non-sensitive toward moisture and oxi-
dation. Also, these compounds can be utilized in various conversions with excellent
selectivity and yields. Besides, organo-catalysts are free of metals, making them an
environmentally friendly and valuable portion of green chemistry [1–4].
Succinimide is a cyclic imide which can be easily prepared from the reaction
of succinic acid with ammonia in the presence of some catalysts. It can also be
prepared by the thermal decomposition of ammonium succinate [5]. Some of its
derivatives such as N-chlorosuccinimide (NCS) [6], N-bromosuccinimide (NBS)
[
7] and N-sulfonated succinimide are very important because that they show pro-
moting eꢂect in special organic transformations [8]. Despite its derivatives, there
is not any report about the promoting catalytic activity of succinimide on its own.
Arylidene malononitrile compounds are important chemical intermediates that
can be obtained via reactions between diꢂerent types of aldehydes and malon-
onitrile. Knoevenagel reaction that is a very important method for the forma-
tion of C=C bonds is a famous reaction to acquire such derivatives. For this rea-
son, various types of the catalysts have been reported for this reaction such as
MNPs–guanidine [9], onion extract [10], CTMAB [11], ZnO [12], [TBA][Leu]
[
13], Ni-NPs [14], Fe O @SiO -3 N [15], taurine [16], hexamethylenetetramine-
3 4 2
bromine [17] and γ-Fe O @SiO @[Bis-APTES]Cl -NPs [18].
2
3
2
2
Multi-component reactions (MCRs) as reactions which by using them three or
more reactants combine via a one-pot reaction to form a single product contain-
ing substantially all of the atoms of the starting materials have been widely used
in medicinal chemistry and drug discovery programs [19], combinatorial chemis-
try [20], natural product synthesis [21] and agrochemistry [22].
Tetrahydrobenzo[b]pyrans are organic compounds that can be utilized as cos-
metic pigments and photoactive materials [23, 24]. Because of their usefulness
and very eꢂective properties, diꢂerent types of methods and catalysts have been
used for the promotion of the synthesis of these compounds via MCRs among
which taurine [16], HDMBAB [25], DBSA [26], I [27], TBAC [28], l-proline
2
[
29], [Ch][OH] [30] and glutamic acid [31] are examples.
Although the reported methods and catalysts for the synthesis of arylidene
malononitriles and tetrahydrobenzo[b]pyrans are useful, most of them suꢂer from
disadvantages including long reaction times, low yields, diꢁculties in the prepa-
ration of the catalyst, non-recyclability of the catalyst, harsh reaction conditions
and so on. Therefore, the introduction of new catalysts which their utilizations are
not included the mentioned drawbacks is still in demand.
In this research, for the ꢀrst time, we designed, synthesized and characterized a
bis-compound of succinimide as a basic catalyst having two active sites and used
1
3

Introduction of a new bis-derivative of succinimide (Bis-Su)…
it in the promotion of the preparation of arylidene malononitrile and benzo[b]
pyran derivatives which are suitable reference reactions to show the ability of the
basic and acidic catalyst.
Experimental
Materials
All chemicals including succinimide (Merck≥98%), 1,4-dichlorobutane (Sigma-
Aldrich≥98%), aldehydes, malononitrile (Sigma-Aldrich≥99%), dimedone (Merck
9
5%) and solvents were purchased from Merck (Munich) and Sigma-Aldrich (Mum-
bai) chemical companies and were used without further puriꢀcation. The purity
determination of the substrates and reaction monitoring was accompanied by TLC
using silica gel SIL G/UV 254 plates. All solvents were kept sealed in airtight bot-
tles as well to minimize the absorption of atmosphere moisturize. Moreover, they
had gotten distilled before being used. Products were characterized by their physi-
cal constants and comparison with authentic samples and those reported in the
literature.
Instrumentation
Melting points were determined using a Buchi B-545 apparatus. The FT-IR spec-
tra were recorded on a PerkinElmer 781 spectrophotometer. The NMR spectrums
were recorded using Bruker Avance 400 MHz and 500 MHz instruments using TMS
(
0.00 ppm) as internal standard and DMSO-d as the solvent.
6
Preparation of 1,1΄‑(butane‑1,4‑diyl)bis(pyrrolidine‑2,5‑dione) (Bis‑Su)
In a 50-mL round-bottomed ꢃask, a mixture of succinimide (0.99 g, 10.0 mmol) and
NaOH (0.4 g, 10.0 mmol) in DMSO (5 mL) was stirred for 2h at 60 °C. After that,
1
1
,4-dichlorobutane (0.54 mL, 5.0 mmol) was added to the mixture and stirred for
0 h at 60 °C until a very viscous solution was formed. After that, it was washed by
diethyl ether for three times (3×5 mL) and ethanol (3×10 mL) to remove any unre-
acted substrates; then, the white solid was obtained. The resulting product was dried
using a vacuum pump (2.42g, yield 93.6%) (Scheme 1) (Fig. 1).
Physical and spectral data of Bis-Su: White solid; M.P. 167–169 °C; FT-IR (KBr,
−1
1
cm ) υ : 3445, 2998,1692, 1401, 666; H NMR (500 MHz, DMSO-d ) (ppm):
max
6
1
3
1
.47–1.52 (m, 4H), 2.69 (s, 8H), 3.40–3.43 (m, 4H); C NMR (125 MHz, DMSO-
d ) (ppm): 25.0, 28.6, 37.9, 178.4.
6
General procedure for the preparation of arylidene malononitrile derivatives
In a 25-mL round-bottomed ꢃask, a mixture of aromatic aldehyde (1.0 mmol),
malononitrile (1.1 mmol) and Bis-Su (0.04 mmol ~ 10 mg), in H O/EtOH [5 mL
2
1
3

F. Hassanzadeh et al.
Scheme 1 Synthesis of 1,1΄-(butane-1,4-diyl)bis(pyrrolidine-2,5-dione) (Bis-Su)
Fig. 1 Synthesized bis-succin-
imide (Bis-Su)
(
1:1)] was stirred at 60 °C for an appropriate time. After completion of the reac-
tion, which was monitored by TLC [n-hexane:EtOAc (7:3)], the mixture was
cooled to room temperature and the solid product was ꢀltered, and washed sev-
eral times with cold distilled water (2 mL) to obtain essentially pure product.
The solid product can be recrystallized from ethanol if necessary (1a–1s).
Spectroscopic data of (E)‑2‑(3‑(2‑nitrophenyl) allylidene)malononitrile [1 s] (new
product)
−
1
Yellow solid; M.P. 191–194 °C; IR (KBr) ν
(cm ) = 3422, 3100, 2927, 2224,
max
1
1
609, 2224, 1571, 1522, 1349; HNMR (400 MHz, DMSO-d ) (δ, ppm) = 7.32
6
(
(
dd, J = 15.0 Hz, J = 11.2 Hz, 1H), 7.79 (dd, J = 8.0 Hz, J = 1.6 Hz, 1H), 7.88
1 2 1 2
dd, J = 15.0 Hz, J = 11.2 Hz, 1H), 7.95 (d, J = 15.0, 1H), 8.16 (tt, J = 8.0 Hz,
1
2
1
1
3
J = 1.2 Hz, 1H), 8.51 (dd, J = 11.6 Hz, J = 0.8 Hz, 1H); CNMR (100 MHz,
2
1
2
1
3

Introduction of a new bis-derivative of succinimide (Bis-Su)…
DMSO-d ) (δ, ppm) = 83.9, 111.8, 113.7, 124.8, 126.5, 128.9, 129.4, 131.8,
6
1
33.9, 144.6, 148.5, 161.3.
General procedure for the preparation of tetrahydrobenzo[b]pyran derivatives
In a 25-mL round-bottomed ꢃask, a mixture of an aromatic aldehyde (1.0 mmol),
malononitrile (1.1 mmol), dimedone (1.0 mmol) and Bis-Su (0.04 mmol ~ 10 mg)
in H O/EtOH [5 mL (1:1)] was stirred at 60 °C for an appropriate time. The reac-
2
tion progress was monitored by TLC [n-hexane: EtOAc (7:3)]. After completion
of the reaction, the mixture was cooled to room temperature and the solid product
was ꢀltered, and washed with cold distilled water (2 mL) to obtain the pure prod-
ucts. The solid product can be recrystallized from ethanol if necessary (2a-2 s).
Spectroscopic data of (E)‑2‑amino‑7,7‑dimethyl‑4‑(2‑nitrostyryl)‑5‑oxo‑5,6,7,8
‑tetrahydro‑4H‑chromene‑3‑carbonitrile [2 s] (new product)
−
1
Pale yellow powder; M.P. 256-258 °C; IR (KBr) ν
(cm ) = 3435, 3334, 2555,
max
1
3
205, 2961, 2193, 1670, 1599, 1529, 1359; HNMR (400 MHz, DMSO-d ) (δ,
6
ppm) = 1.01 (s, 3H), 1.05 (s, 3H), 2.19–2.47 (m, 4H), 3.88 7.79 (d, J = 6.8 Hz,
1
2
7
H), 6.27 (dd, J = 15.6 Hz, J = 6.8 Hz, 1H), 6.67 (d, J = 15.6 Hz, 1H), 7.16 (s,
1 2
H), 7.49 (td, J = 7.6 Hz, J = 16 Hz, 2H), 7.65 (td, J = 7.6 Hz, J = 5.6 Hz, 1H),
1
2
1
2
.73 (dd, J = 8.0 Hz, J = 1.6 Hz, 1H), 7.92 (dd, J = 8.0 Hz, J = 1.2 Hz, 1H);
1
2
1
2
1
3
CNMR (100 MHz, DMSO-d ) (δ, ppm) = 26.7, 28.3, 31.8, 32.7, 49.9, 54.3,
6
1
11.4, 123.5, 124.2, 127.9, 130.8, 133.2, 136.6, 147.6, 159.4, 162.7, 195.8.
Results and discussion
In this study and in continuation of our previous works on the introduction of
various catalysts for the promotion of organic reactions [32–37], we wish to
introduce bis-succinimide, a cheap, non-toxic and easily preparable catalyst from
available reagent, as an eꢂective accelerator for the above-mentioned target mol-
ecules. It should be mentioned that the use of this reagent is not accompanied by
considerable drawbacks.
Regarding our research, the basic catalysts often have better performance when
a component of a reaction is malononitrile. Since a basic catalyst can quickly
remove the acidic hydrogen of the malononitrile, negatively charged carbon
forms fast and enters the reaction. To prove this, we also used succinimide as the
catalyst in the optimized reaction condition for Bis-Su which has relatively acidic
hydrogen. It was observed that the use of Bis-Su has distinguished advantages
from the viewpoints of catalyst amount in the reaction and also the rate of the
1
3

F. Hassanzadeh et al.
reaction. Therefore, the design and preparation of Bis-Su from the succinimide
that not only is a basic reagent in its nature, but has two active catalytic sites in
its structure that results in much higher performance in the reaction compared to
succinimide are a valuable promotion in this new presented methodology.
Characterization of the catalyst
After the preparation of Bis-Su, various spectroscopic techniques were used to
characterize the structure of the compound. Here are some elucidations in detail:
FT‑IR and NMR analysis
The comparison of FT-IR spectrum of succinimide and bis-succinimide shows
the presence of similar functional groups in both of the reactions. It should be
−
1
−1
emphasized that noticeable absorption bands at 2992 cm and 2948 cm in the
FT-IR spectrum of Bis-Su are related to the stretching vibrations of the methylene
groups of the linker. Also, the number of peaks in the FT-IR of Bis-Su is consid-
erably decreased. This result can be attributed to the limitation of the vibration
modes due to the locking of the rings in the prepared reagent.
1
In the H NMR spectrum of 1,1′-(butane-1,4-diyl)bis(pyrrolidine-2,5-dione)
as a symmetric compound, three peaks related to three types of hydrogen are
observable. Two multiplet peaks (H and H ) in the areas of 1.47–1.52 ppm and
a
b
3
.40–3.43 ppm are related to the hydrogens of methylene groups of the linker.
Besides, a single peak at 2.69 ppm (H ) is related to the methylene groups of suc-
c
cinimide rings.
1
3
C NMR also shows four peaks related to four diꢂerent carbons. The peaks at
2
5.0 ppm 28.6 ppm (C and C ) are related to the middle methylene groups of the
1
3
linker. The peak at 37.9 ppm (C ) is attributed to methylene groups of the succin-
3
imide, while the peak at 178.4 ppm (C ) is related to carbonyl groups of the rings.
4
Catalytic activity
Optimization of the reaction conditions in the synthesis of arylidene malononitrile
derivatives
For the optimization of the reaction conditions of preparation of arylidene malo-
nonitrile derivatives, the reaction of 4-chlorobenzaldehyde and malononitrile was
selected as a model reaction for the synthesis and it was investigated under the
eꢂect of diꢂerent factors including the temperature, amounts of the catalyst, sol-
vent (dichloromethane, acetonitrile, ethanol, DMSO, H O and EtOH/H O) and
2
2
also solvent-free conditions. As given in Table 1, the best results can be obtained
1
3

Introduction of a new bis-derivative of succinimide (Bis-Su)…
Table 1 Optimization of the reaction conditions for the preparation of arylidene malononitrile derivative
of 4-chlorobenzaldehyde
Entry
Catalyst (mg)
Solvent
Temperature (°C)
Time (min.)
Yield (%)
30a
b
1
2
3
4
5
6
7
8
9
No catalyst
H O/EtOH
Reꢃux
Reꢃux
Reꢃux
Reꢃux
Reꢃux
Reꢃux
Reꢃux
Reꢃux
40
50
60
80
Reꢃux
60
100
100
100
100
100
100
100
60
100
35
12
12
10
2
c
10
10
10
10
10
10
10
10
10
10
10
10
20
5
n-Hexane
DMSO
CH Cl
Trace
Tracec
Tracec
2
2
c
CHCl3
Trace
c
CH CN
40
3
c
EtOH
55
H O
81
65
2
b
b
b
b
b
b
b
c
H O/EtOH
2
10
11
12
13
14
15
H O/EtOH
84
97
92
87
85
80
2
H O/EtOH
2
H O/EtOH
2
H O/EtOH
2
H O/EtOH
30
24
2
H O/EtOH
60
2
a
Reaction conditions: 4-Chlorobenzaldehyde (1.0 mmol), malononitrile (1.1 mmol), solvent (5 mL) and
required amounts of the catalyst
b
(
1:1)
c
Reaction was not completed
Scheme 2 Synthesis of arylidene malononitrile derivatives
when 10 mg of bis-succinimide is used in a mixture of H O and EtOH (1:1) at
2
6
0 °C (Table 1, entry 11; Scheme 2).
After the optimization of the reaction conditions, various aromatic aldehydes
containing electron-releasing, electron-withdrawing and halogen substituents on
their aromatic rings were examined to prepare the corresponding arylidene malo-
nonitrile derivatives. Using this method, no considerable eꢂect of the substituent
was observed and the desired products were obtained in high yields during short
reaction times (Table 2).
After the successful performance of Bis-Su in the condensation of aldehydes
with malononitrile, we were interested to investigate its ability in the promotion
1
3

F. Hassanzadeh et al.
Table 2 Synthesis of arylidenlidene malononitrile derivatives in the presence of Bis-Su as the catalyst
Entry Aldehyde
Product Time (min.) Yield (%) M.p. (°C)
Obs.
Lit. [References]
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
C H CHO
1a
1b
1c
1d
1e
1f
1 g
1 h
1i
30
16
20
18
16
20
20
30
12
15
18
27
37
32
40
28
32
26
35
86
89
93
85
96
90
95
92
97
94
89
93
95
79
90
88
76
89
91
81–84
90–92
136–138 139–140 [9]
81–82
93–95
82–84 [11]
93–94 [38]
6
5
2-ClC H CHO
6
4
2-NO C H CHO
2
6
4
2-OCH C H CHO
80 [39]
95–97[18]
3
6
4
3-ClC H CHO
6
4
3-OCH C H CHO
106–108 107–108 [40]
102–104 103–105 [38]
156–158 155–156 [14]
159–161 161–162 [38]
157–159 159–160 [9]
123–125 122–124 [41]
156–158 157–160 [42]
185–187 186–188 [38]
111–112 112–114 [42]
137–139 137–138 [39]
188–190 190–191 [40]
194–196 195–197 [16]
123–125 124–126 [42]
191–194 New
3
6
4
3-NO C H CHO
2
6
4
3-BrC H CHO
6
4
4-ClC H CHO
6
4
0
1
2
3
4
5
6
7
8
9
4-BrC H CHO
1j
6
4
4-FC H CHO
1 k
1 l
1 m
1n
1o
1p
1r
6
4
4-NO C H CHO
2
6
4
4-OHC H CHO
6
4
4-OCH C H CHO
3
6
4
4-CH C H CHO
3
6
4
4-NMe C H CHO
2
6
4
3-Phenylpropanal
Cinnamaldehyde
2-Nitrocinnamaldehyde 1 s
1q
aYields are related to isolated products
of one-pot three-component synthesis of tetrahydrobenzo[b]pyran derivatives as
the other biologically important organic compounds.
For the optimization of the reaction conditions, the reaction of a mixture of
4
-chlorobenzaldehyde and malononitrile with dimedone (as a model for the synthe-
sis of tetrahydrobenzo[b]pyrans) was studied under the inꢃuence of diꢂerent fac-
tors including the temperature, amounts of the catalyst and solvent and also in the
absence of solvent. The collected data in Table 3 show that the best results can be
obtained in a mixture of H O and EtOH (1:1) at 80 °C, in the presence of 10 mg of
2
the catalyst was used in the above-mentioned reactions, respectively (Table 3, entry
1
2; Scheme 3).
In continue, variety of aromatic aldehydes were used for the synthesis of
benzo[b]pryan derivatives in the optimized condition. The obtained results clari-
ꢀ
ed that under the selected conditions, all the expected products were obtained
in high yields during acceptable reaction times (Table 4).
The reusability of Bis-Su in the studied reactions was also checked by choosing
the model reactions (Table 2, 1i, and Table 4, 2i) and repeating them ꢀve times
1
3

Introduction of a new bis-derivative of succinimide (Bis-Su)…
Table 3 Optimization of the reaction conditions for the preparation of tetrahydrobenzo[b]pyran deriva-
tive of 4-chlorobenzaldehyde
Entry
Catalyst (mg)
Solvent
Temperature (°C)
Time (min.)
Yield (%)
50b
a
1
2
3
4
5
6
7
8
9
No catalyst
H O/EtOH
Reꢃux
Reꢃux
Reꢃux
Reꢃux
Reꢃux
Reꢃux
Reꢃux
Reꢃux
50
60
70
80
Reꢃux
80
100
100
100
100
100
100
100
80
37
50
35
20
2
b
10
10
10
10
10
10
10
10
10
10
10
10
5
n-hexane
DMSO
CH Cl
Trace
Tracec
Traceb
2
2
b
CHCl3
Trace
b
CH CN
50
3
b
EtOH
55
H O
88
47
54
2
a
a
a
a
a
a
a
b
H O/EtOH
2
b
10
11
12
13
14
15
H O/EtOH
2
H O/EtOH
78
93
87
84
72
2
H O/EtOH
2
H O/EtOH
20
33
28
2
H O/EtOH
2
15
H O/EtOH
80
2
Reaction conditions: 4-Chlorobenzaldehyde (1.0 mmol), dimedone (1.0 mmol), malononitrile
(
1.1 mmol), solvent (5 mL) and required amount of the catalyst
a
(
1:1)
b
Reaction was not completed
Scheme 3 Synthesis of tetrahydrobenzo[b]pyran derivatives
in the ꢀltrated solution without the addition of any amounts of the fresh catalyst.
It was observed that the stability of Bis-Su was excellent in the studied reactions
(
Fig. 2).
The purposed mechanism of the studied reactions in the presence of bis-suc-
cinimide as a basic catalyst is shown in Scheme 4. According to this mechanism,
at the ꢀrst step, malononitrile is activated by the lone pair electrons of nitro-
gen atoms of bis-succinimide rings. Then, it attacked the carbonyl group of the
aldehydes which was activated by the conjugated acid of the catalyst. Elimina-
tion of a molecule of water led to arylidene malononitrile products (1a–1s). In
1
3

F. Hassanzadeh et al.
Table 4 Synthesis of tetrahydrobenzo[b]pyran derivatives in the presence of Bis-Su as the catalyst
Entry Aldehyde
Product Time (min.) Yield (%)a M.p. (°C)
Obs.
Lit. [References]
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
C H CHO
2a
2b
2c
2d
2e
2f
2g
2h
2i
2j
2k
2l
2m
2n
2o
2p
2r
35
23
32
35
28
30
30
34
20
24
22
31
42
30
50
45
40
29
30
84
93
92
83
95
90
92
94
93
95
91
93
93
87
90
86
85
90
89
231–233 232–234 [43]
209–211 211–213 [43]
227–229 228 [44]
6
5
2-ClC H CHO
6
4
2-NO C H CHO
2
6
4
2-OCH C H CHO
194–196 196–199 [43]
227–229 228–230 [45]
188–189 188–190 [45]
213–214 211–213 [45]
287–289 289–291 [45]
210–212 208–210 [43]
200–202 201–203 [43]
212–214 214–215 [43]
181–183 181–183 [43]
222–224 222–224 [46]
197–199 196–198 [46]
217–218 217–219 [46]
195–197 197–199 [47]
196–198 199–200 [48]
203–205 205–207 [49]
255–257 New
3
6
4
3-ClC H CHO
6
4
3-OCH C H CHO
3
6
4
3-NO C H CHO
2
6
4
3-BrC H CHO
6
4
4-ClC H CHO
6
4
0
1
2
3
4
5
6
7
8
9
4-BrC H CHO
6
4
4-FC H CHO
6
4
4-NO C H CHO
2
6
4
4-OHC H CHO
6
4
4-OCH C H CHO
3
6
4
4-CH C H CHO
3
6
4
4-NMe C H CHO
2
6
4
3-Phenylpropanal
Cinnamaldehyde
2-Nitrocinnamaldehyde 2s
2q
aYields are related to isolated products
Fig. 2 Reusability of the catalyst in the synthesis of arylidene malononitrile and tetrahydrobenzo[b]pyran
derivatives of 4-chlorobenzaldehyde
1
3

Introduction of a new bis-derivative of succinimide (Bis-Su)…
Scheme 4 Plausible pathway of the studied reactions
the presence of dimedone, intermediates (II) are produced which after cycliza-
tion forms intermediate (III) and a subsequent imine-enamine tautomerization
resulted in the corresponding tetrahydrobenzo[b]pyran derivatives (2a–2s). The
role of Bis-Su as a basic organo-catalyst is shown well in all steps of the pro-
posed mechanism.
To show the catalytic ability of bis-succinimide in the studied reactions, a
comparison between Bis-Su and other types of catalysts for all of the above-
mentioned reactions is presented in Table 5. Based on this table, it can be con-
cluded that the reaction in the presence of Bis-Su can be preferred than most of
the previously reported ones regarding the catalyst amounts, reaction times and
yields.
1
3

F. Hassanzadeh et al.
Table 5 Comparision between the ability of some catalysts and bis-succinimide in the mentioned reac-
tions
Product
Catalyst
Amount Conditions
Time (min.) Yield (%) [References]
MNPs–guani-
dine
Onion extract
CTMAB
ZnO
5 mg
PEG-H O
150
96
[9]
2
(1:1)/r.t.
S.F/r.t.
2 mL
182 mg H O/r.t
500 mg H O/r.t
9 mg
10 mg
50 mg
120
90
90
60
45
20
90
94
86
97
94
90
[10]
[11]
[12]
[13]
[14]
[15]
2
2
[
TBA][Leu]
H O/50 °C
2
Ni-NPs
S.F./70 °C
Toluene/75 °C
Fe O @
3
4
SiO -3 N
2
Bis-Su
10 mg
46 mg
H O-EtOH
12
97
90
[This work]
[25]
2
(
1:1)60 °C
HDMBAB
H O/80–90 °C
450
2
DBSA
I2
TBAC
l-proline
65 mg
25 mg
28 mg
12 mg
10 mg
30 mg
10 mg
H O/reꢃux
DMSO/120 °C
240-420
210
120
120
60
40
20
69
72
98
72
86
91
93
[26]
[27]
[28]
[29]
[30]
[31]
This Work
2
H O/reꢃux
2
EtOH/reꢃux
[
Ch][OH]
H O/80 °C
2
Glutamic acid
Bis-Su
EtOH/reꢃux
H O-EtOH
2
(
1:1)80 °C
Conclusions
In this article, we have synthesized and characterized bis-succinimide (Bis-Su) as a
basic organo-catalyst and used it in the synthesis of biologically and pharmacologi-
cally active arylidene malononitrile and tetrahydrobenzo[b]pyran derivatives under
mild conditions. The most important advantages of this method are included the use
of non-toxic cheap organo-catalyst, mild conditions, excellent yields of the products,
short reaction times, simple workup procedure and reusability of the catalyst.
Acknowledgements We are thankful to the Research Council of the University of Guilan for the partial
support of this research.
References
1
2
.
.
G. Harald, Organocatalysis. 2, 141 (2008)
I.R. Shaikh, J. Catal. 2014, 1 (2014)
1
3

Introduction of a new bis-derivative of succinimide (Bis-Su)…
3
.
S. Chandrasekhar, N.R. Reddy, S.S. Sultana, C. Narsih-mulu, K.V. Reddy, Tetrahedron 62, 338
(
2006)
4
5
6
.
.
.
P.I. Dalko, L. Moisan, Angew. Chem. Int. Ed. 43, 5138 (2004)
H.T. Clarke, L.D. Behr, Org. Syn. Coll. 16, 75 (1936)
F. Zentz, A. Valla, R.L. Guillou, R. Labia, A.G. Mathot, D. Sirot, Int. J. Pharm. Pharm. Sci. 6, 8
(
2014)
7
.
B.G. Hazra, V.S. Pore, S.K. Day, S. Datta, M.P. Darokar, D. Saikia, Bioorg. Med. Chem. Lett. 14,
7
73 (2004)
8
9
.
.
S. Fujisaki, S. Hamura, H. Eguchi, A. Nishida, Bull. Chem. Soc. Jpn. 66, 2426 (1993)
A. Rostami, B. Atashkar, H. Gholami, Catal. Commun. 37, 69 (2013)
1
1
1
1
1
1
1
1
1
1
2
2
2
0. P. Kaliyan, S. Matam, S.P. Muthu, Asian J. Green Chem. 3, 125 (2019)
1. S. Wang, Z. Ren, W. Cao, W. Tong, Synth. Commun. 31, 673 (2001)
2. M. Basude, P. Sunkara, V.S. Puppala, J. Chem. Pharm. Res. 9, 46 (2013)
3. P. Ossowicz, Z. Rozwadowski, M. Gano, E. Janus, Pol. J. Chem. 18, 90 (2016)
4. R.G. Chaudhary, J.A. Tanna, N.V. Gandhare, A.R. Rai, H.D. Juneja, Adv. Mater. Lett. 6, 990 (2015)
5. R. Vaid, M. Gupta, Monatsh. Chem. 146, 645 (2015)
6. F. Shirini, N. Daneshvar, RSC Adv. 6, 110190 (2016)
7. M.M. Heravi, H.A. Oskooie, Z. Latiꢀ, H. Hamidi, Adv. J. Chem. A. 1, 7 (2018)
8. R. Karimi-Chayjani, N. Daneshvar, F. Shirini, Res. Chem. Intermed. 45, 2471 (2019)
9. E. Ruijter, R.V.A. Orru, Drug Discov Today Technol. 10, 15 (2013)
0. W.H. Moos, C.R. Hurt, G.A. Morales, Mol. Divers. 13, 241 (2009)
1. B.B. Touré, D.G. Hall, Chem. Rev. 109, 4439 (2009)
2. C. Lamberth, A. Jeanguenat, F. Cederbaum, A. De Mesmaeker, M. Zeller, H.J. Kempf, R. Zeun,
Bioorg. Med. Chem. 16, 1531 (2008)
2
2
3. R. Kakuchi, Angew. Chem. Int. Ed. 53, 46 (2014)
4. G.P. Ellis, (Chromenes, chromanones, and chromones, Chemistry of Heterocyclic Compounds
Chromenes, A. Weissberger and E. C. Taylor, Eds., chapter 2, pp. 11–139, John Wiley, New
York, NY, USA, 1977)
2
2
2
5. T.S. Jin, A.Q. Wang, F. Shi, L.S. Han, L.B. Liu, T.S. Li, ARKIVOC. (xiv), 78 (2006)
6. E. Sheikhhosseini, D. Ghazanfari, V. Nezamabadi, Iran. J. Catal. 3, 197 (2013)
7. R.S. Bhosale, C.V. Magar, K.S. Solanke, S.B. Mane, S.S. Choudhary, R.P. Pawar, Synth. Com-
mun. 37, 4353 (2007)
2
2
3
3
3
3
8. H. Mehrabi, N. Kamali, J. Iran. Chem. Soc. 9, 599 (2012)
9. F.K. Behbahani, F. Alipour, Guyana J. Sci. 28, 387 (2015)
0. H. Hu, F. Qiu, A. Ying, J. Yang, H. Meng, Int. J. Mol. Sci. 15, 6897 (2014)
1. F. Hatamjafari, J. Chem. Health Risks. 6, 133 (2016)
2. N. Daneshvar, M.S.N. Langarudi, R. Karimi-Chayjani, F. Shirini, Bioorg. Chem. 77, 68 (2018)
3. N. Daneshvar, M. Nasiri, M. Shirzad, M.S.N. Langarudi, F. Shirini, H. Tajik, New J. Chem. 42,
9
744 (2018)
3
4. N. Daneshvar, O. Goli-Jelodar, R. Karimi-Chayjani, M. Safarpoor Nikoo Langarudi, F. Shirini,
Chemistry Select. 4, 1562 (2019)
3
3
3
5. Z. Shariꢀ, N. Daneshvar, M.S.N. Langarudi, F. Shirini, Res. Chem. Intermed. 45, 4941 (2019)
6. S. Darvishzad, N. Daneshvar, F. Shirini, H. Tajik, J. Mol. Struct. 1178, 420 (2019)
7. R. Karimi-Chayjani, N. Daneshvar, M.S.N. Langarudi, F. Shirini, H. Tajik, J. Mol. Struct. 1199,
1
26891 (2020)
3
3
4
8. S.L. Khillare, A.O. Dhokte, M.K. Lande, B.R. Arbad, Int. J. Chem. 5, 96 (2014)
9. M.M. Heravi, K. Bakhtiari, H.A. Oskooi, J. Chin. Chem. Soc. 54, 579 (2007)
0. M.M.H. Bhuiyan, M.I. Hossain, M. Ashraful Alam, M.M. Mahmud, Chemistry Journal. 2, 30
(
2012)
4
4
4
4
4
4
1. A. Pasha, M. Manjula, P. Krishnappa, V. Jayashankara, Indian J. chem. 49B, 1428 (2010)
2. P. Gupta, M. Kour, S. Paul, J.H. Clark, RSC Adv. 4, 7461 (2014)
3. F. Shirini, O. Goli-Jolodar, M. Akbari, M. Seddighi, Res. Chem. Intermed. 42, 4733 (2016)
4. S.R. Kamat, A.H. Mane, S.M. Arde, R.S. Salunkhe, Int. J. Pharm. 4, 1012 (2014)
5. M.R. Islami, E. Mosaddegh, Phosphorus. Sulfur Silicon Relat. Elem. 184, 3134 (2009)
6. K.S. Pandit, P.V. Chavan, U.V. Desai, M.A. Kulkarni, P. Wadgaonkar, New J. Chem. 36, 4452
(
2015)
1
3

F. Hassanzadeh et al.
4
7. P.P. Salvi, A.M. Mandhare, A.S. Sartape, D.K. Pawar, S.H. Han, S. Kolekar, S.C.R. Chim. 14, 878
(
2011)
4
4
8. V.D. Dyachenko, A.N. Chernega, Russ. J. Org. Chem. 43, 60 (2007)
9. S. Gurumurthi, V. Sundari, R. Valliappan, E.-J. Chem. 6, S466 (2009)
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