An affordable DABCO-based ionic liquid efficiency in the synthesis of 3-amino-1-aryl-1H-benzo[f] chromene-2-carbonitrile, 1-(benzothiazolylamino)phenylmethyl-2-naphthol, and 1-(benzoimidazolylamino)phenylmethyl-2-naphthol derivatives

Article abstract of DOI:10.1007/s13738-018-1408-x

In this study, [H₂-DABCO][HSO₄]₂ is applied as an acidic ionic liquid to exclude some disadvantages of former methods reported for the synthesis of 3-amino-1-aryl-1H-benzo[f]chromene-2-carbonitrile, 1-(benzothiazolylamino)

Full text of DOI:10.1007/s13738-018-1408-x

Journal of the Iranian Chemical Society
https://doi.org/10.1007/s13738-018-1408-x
ORIGINAL PAPER
An affordable DABCO-based ionic liquid efficiency
in the synthesis of 3-amino-1-aryl-1H-benzo[f] chromene-2-
carbonitrile, 1-(benzothiazolylamino)phenylmethyl-2-naphthol,
and 1-(benzoimidazolylamino)phenylmethyl-2-naphthol derivatives
Nazanin Nabinia1 · Farhad Shirini1 · Hassan Tajik1 · Maryam Mashhadinezhad1 ·
Mohaddeseh Safarpoor Nikoo Langarudi1
Received: 13 February 2018 / Accepted: 21 May 2018
© Iranian Chemical Society 2018
Abstract
In this study, [H2-DABCO][HSO4]2 is applied as an acidic ionic liquid to exclude some disadvantages of former methods
reported for the synthesis of 3-amino-1-aryl-1H-benzo[f]chromene-2-carbonitrile, 1-(benzothiazolylamino)phenylmethyl-
2-naphthol, and 1-(benzoimidazolylamino)phenylmethyl-2-naphthol derivatives. In the presence of this catalyst, all reactions
are performed under neat conditions during short reaction times in good-to-high yields. Ease of preparation and recyclability
of the catalyst are the other important advantages of this method.
Keywords Acidic ionic liquid · 1,4-Diazobicyclo[2,2,2] octane (DABCO) · 3-Amino-1-aryl-1H-benzo[f] chromene-2-
carbonitrile derivatives · 1-(Benzothiazolylamino)phenylmethyl-2-naphthol · 1-(Benzoimidazolylamino)phenylmethyl-2-
naphthol derivatives · Multi-component reaction
Introduction
such as antibacterial [2], anticancer [3–5], antimicrobial [6,
7], antiviral [8, 9], and central nervous system (CNS) [10]
activities.
According to global environmental concern and green chem-
istry roles, its important issue to using less hazardous chemi-
cal solvents, reduce waste materials, and apply catalysis in
organic reactions. One of the powerful synthetic tools that
use to develop preparation of some organic compounds is
multi-component reactions (MCRs). The importance of this
category of reactions is that they can facilitate synthesis of
some important heterocyclic and bioactive compounds in
just one straightforward step; moreover, these reactions are
in correlation with some green chemistry principles [1].
2-Amino-4H-chromene, and benzimidazole and benzothia-
zole derivatives are two important classes of heterocyclic
compounds that can be synthesized via this strategy.
Benzimidazole and benzothiazole derivatives are a group
of attractive heterocyclic pharmacophores which demon-
strate a wide range of biological properties, including anti-
microbial, antibacterial, antitumor, anticancer, anti-inflam-
matory, and analgesic [11–25] activities. These compounds
also are known in drugs designed for targeting DNA and
DNA-associated processes [26]. In addition, benzimidazole
nucleus exists in some natural bioactive compounds like
vitamin B12.
Because of the above-mentioned important properties
many of methods have been reported for the synthesis of
2-amino-4H-chromene, benzimidazole and benzothiazole
derivatives [27–33]. These methods are also useful, but most
of them suffer from disadvantages such as harsh reaction
conditions, waste primary materials, use of toxic solvents,
and long reaction conditions.
Compounds, which possess 2-amino-4H-chromene
structure moiety, are important heterocycles because of
their remarkable biological and pharmacological properties
Nowadays, due to the significant properties of ionic liquids,
scientists have developed the applications of these compounds
as green solvents and potential catalysts in various fields. Ionic
liquids have attracted attentions because that their unique
* Farhad Shirini
shirini@guilan.ac.ir; fshirini@gmail.com
1
Department of Chemistry, College of Science, University
of Guilan, Rasht 41335-19141, Iran
Vol.:(0123456789)
1 3

Journal of the Iranian Chemical Society
physical properties such as low viscosity, non-volatile, high
solubility capability, and ease of preparation made them dif-
ferent from ordinary solvents [34, 35]. In addition, they can
be prepared easily from commercially available materials. In
this study and in continuation of our research group successive
efforts in the synthesis of novel ionic liquid catalysts [36–41]
and to solve the restrictions which have been observed in the
synthesis of 3-amino-1-aryl-1H-benzo[f] chromene-2-carbon-
itrile, 1-(benzothiazolylamino)phenylmethyl-2-naphthol, and
1-(benzoimidazolylamino)phenylmethyl-2-naphthol deriva-
tives, we wish to report the applicability of our recently intro-
duced acidic DABCO-based ionic liquid [42] in the accelera-
tion of the synthesis of these types of compounds.
All solvents were prepared from Merck Chemical Company
(Munich) and were kept in isolated conditions as well to
minimize the absorption of atmosphere moisture. Moreo-
ver, they had gotten distilled before being used. Products
were characterized by their physical constants, comparison
with reported in the literature samples and IR and NMR
spectroscopy.
Melting points were measured by electrothermal IA9100
melting point apparatus in capillary tubes. The starting tem-
perature of the approximate melting range was input via the
keyboard and the melting point range was spotted visually.
FT-IR spectra were recorded on a Perkin-Elmer spectrum
BX series and KBr pellets were used for solid samples. 1H
NMR and 13C NMR spectra were determined on Bruker
AV-400 using TMS (0.00 ppm) as internal standard and
DMSO-d6 as solvent.
Experimental
General
Preparation of 1,4‑diazabicyclo[2.2.2]
octane‑1,4‑diium hydrogen sulfate {[H2‑DABCO]
[HSO4]2} [39]
All the chemicals were used in this procedure including
aldehydes, 2-naphthol, malononitrile, 2-aminobenzimida-
zole, and 2-aminobenzothiazole were purchased from Merck
Chemical Company (Munich) and were used without fur-
ther purification. The purity determination of the substrates
and reactions was monitored by thin-layer chromatography
(TLC) on silica-gel polygram SILG/UV 254 Plates.
In a 100 mL round-bottomed flask, 1,4-diazabicyclo[2.2.2]
octane (DABCO) (1.05 g, 9.4 mmol) was dissolved in 50 mL
dry dichloromethane. Then, this mixture was stirred in an
ice-bath for 1 min and a stoichiometric amount of sulfuric
acid (99.99%, 1 mL, 18.8 mmol) was added drop-wise to
it within 25 min. Then, the mixture was heated to reflux
with constant stirring for 24 h. In continue, the solvent
was decanted and the resulting white solid was frequently
washed with diethyl ether (3×15 ml2) to obliterate non-ionic
DABCO (CAS: 280-57-9, MW: 112.17 g/gmol,
assay ≥ 99% w/w %) and sulfuric acid (CAS: 7664-93-9,
MW: 98.08 g/gmol, assay≥ 99.99 v/v %) were purchased
from Sigma-Aldrich Company (Mumbai). Both assays
were reported by company and were not examined more.
Table 1 Optimization of
the amount of the catalyst,
temperature, and solvent in
the synthesis of 3-amino-1-
(4-chlorophenyl)-1H-benzo[f]
chromene-2-carbonitrile
(5b) [entries 1–8] and
Entry Catalyst (mol%) Solvent
Temp. (°C) Time (min.) Conversion [Yield (%)]a
1
2
3
4
5
6
7
8
–
–
–
H2O
–
100
Reflux
100
90
90
60
40
90
90
25
5
Trace
Trace
Not completed
100(75)
Not completed
Not completed
100(93)
0.0048
0.0048
0.0048
0.0065
0.0065
0.0097
–
–
120
1-benzothiazolylamino-(4-
chlorophenylmethyl)-2-naphthol
(6b) [entries 9–18]
H2O
H2O
–
–
–
Reflux
Reflux
100
100
100(96)
9
100
Reflux
90
90
90
90
90
90
90
50
30
15
Trace
Trace
Trace
Not completed
Not completed
100(73)
100(70)
100(85)
10
11
12
13
14
15
16
17
18
–
–
H2O
H2O:C2H5OH (1:1) 80
0.0065
0.0065
0.0065
0.0065
0.0065
0.0065
0.0097
C2H5OH
CH3CN
H2O
Reflux
Reflux
Reflux
H2O:C2H5OH (1:1) 80
–
–
–
100
120
120
100(90)
100(95)
aIsolated yields
1 3

Journal of the Iranian Chemical Society
residues. After that, the obtained ionic liquid was dried
under vacuum to achieve [H2-DABCO][HSO4]2 in 95%
yield (2.74 g) (Scheme 1). The purity of the product was
3-Amino-1-(2-fluorophenyl)-1H-benzo[f] chromene-
2-carbonitrile (5 l). Mp=286–288 °C; IR (KBr) νmax/cm−1:
3440, 3342, 3089, 2921, 2180, 1645,1586, 1482, 1410,
1
1
determined by melting point, Mass, FT-IR, H NMR, and
1228, 1178, 810, 751; H NMR (400 MHz, DMSO-d6)
13C NMR.
δ=7.95 (d, J=9.2 Hz, 1H), 7.93 (d, J =9.2 Hz, 1H), 7.77
(d, J = 8 Hz, 1H), 7.41–7.51 (td, J1 = 7.6 Hz, J2 = 1.2 Hz,
2H), 7.34 (d, J=9.2 Hz, 1H), 7.16–7.25 (m, 3H), 7.09 (ddd,
J1 = 13.4 Hz, J2 = 12 Hz, J3 = 1.2 Hz, 3H), 5.54 (s, 1H);
Spectral data for [H2-DABCO][HSO4]2: white solid;
M.p. 65 °C; MS: m/z=308(M+); FT-IR (KBr, cm−1) vmax
:
1
3400–2400, 1229, 1165, 849, 576; H NMR (400 MHz,
DMSO-d6): δ (ppm) 3.59 (s, 6H), 6.64 (s, 1H, NH), 13.88 (s,
1H, HSO4); 13C NMR (100 MHz, DMSO-d6): δ (ppm) 43.4.
1
13C NMR (100 MHz, DMSO-d6): δ 160.6, 159.8 (d, JCF
= 244 Hz), 147.5, 132.4, 132.3, 131.2, 130.5, 130.2, 130.1,
3
129.3(d, JCF = 7 Hz), 129.1, 127.8, 125.4, 123.1, 120.7,
General procedure for the synthesis
of 3‑amino‑1‑aryl‑1H‑benzo[f]
chromene‑2‑carbonitrile derivatives
117.2, 116.2 (d, 2JCF = 21 Hz), 114.7, 56.4, 32.9 ppm.
General procedure for the synthesis of 1-(benzothia-
zolylamino)phenylmethyl-2-naphthol and 1-(benzoimida-
zolylamino)phenylmethyl-2-naphthol derivatives.
To a mixture of the requested aromatic aldehyde 1
(1 mmol), 2-naphthol 2 (1 mmol) and 2-aminobenzimida-
zole/or 2-aminobenzothiazole 4 (1 mmol), [H2-DABCO]
[HSO4]2 (0.030 g, 0.097 mmol) was added, and then, the
mixture was stirred at 120 °C for an appropriate time. The
progress of the reaction was monitored by TLC [ethyl ace-
tate: n-hexane (3:7)]. After completion of the reaction, the
precipitate was filtered and washed with water to separate
the catalyst. Finally, the crude products were purified by
recrystallization from ethanol to obtain the pure product
(6a–6m).
In a 25 mL round-bottom flask, a mixture of the requested
aromatic aldehyde 1 (1 mmol), 2-naphthol 2 (1 mmol), malo-
nonitrile 3 (1 mmol), and [H2-DABCO][HSO4]2 (0.030 g,
0.097 mmol) was stirred under solvent-free conditions at
100 °C for a certain time. After completion of the reaction,
as identified by TLC [ethyl acetate:n-hexane (3:7)], the solid
product was filtered and washed with water to separate the
catalyst. Then, the precipitate was recrystallized from etha-
nol to obtain the pure product (5a–5l). The spectral data of
the new compound are as follows.
Scheme 1 Preparation of
-
HSO4
[H2-DABCO][HSO4]2
H
o
N
N
N
H
1. 2SO4 (99.99% v/v), 0
CH
2Cl2
C,
N
2. Reflux, 24 h
H
-
HSO4
Ar
CN
NH2
[H2-DABCO][HSO ]
4 2 (0.097 mmol, 0.030 g)
CN
CN
O
5
Solvent-free, 100 °C
O
1
3
OH
+
R
H
2
X
X
N
R
NH
NH2
[H2-DABCO][HSO ]
4 2 (0.097 mmol, 0.030 g)
HN
OH
4
Solvent-free, 120 °C
X=N, S
6
Scheme 2 Synthesis of 3-amino-1-aryl-1H-benzo[f] chromene-2-carbonitrile (5), 1-(benzothiazolylamino)phenylmethyl-2-naphthol, and 1-(ben-
zoimidazolylamino)phenylmethyl-2-naphthol (6) derivatives in the presence of [H2-DABCO][HSO4]2 as the catalyst
1 3

Journal of the Iranian Chemical Society
Table 2 Synthesis of 3-amino-1-aryl-1H-benzo[f] chromene-2-carbonitrile, 1-(benzothiazolylamino)phenylmethyl-2-naphthol and 1-(benzoimi-
dazolylamino)phenylmethyl-2-naphthol derivatives using [H2-DABCO][HSO4]2 as the catalyst
Refe
renc
es
M.P. ( C)
Reported
Time
Yield
Entry Aldehyde
Product
(min.) (%)a
Found
1
2
3
4
C6H5CHO
5a
5b
5c
5d
5
5
5
8
93
96
95
94
275–277 279–280
208–210 207–208
268–270 271–272
237–239 238–240
[43]
[44]
[43]
[44]
4-ClC6H4CHO
2-ClC6H4CHO
4-BrC6H4CHO
5
4-FC6H4CHO
5e 12
91
91
93
227–229 228–229
235–237 235–236
170–172 176–178
[43]
[43]
[43]
6
3-NO2C6H4CHO
4-NO2C6H4CHO
5f
10
7
5g
8
1 3

Journal of the Iranian Chemical Society
Table 2 (continued)
Refe
renc
es
M.P. ( C)
Reported
Time
Yield
Entry Aldehyde
Product
(min.) (%)a
Found
8
4-OHC6H4CHO
5h 15
90
283–285 288–290
[45]
9
4-OCH3C6H4CHO
2-OCH3C6H4CHO
4-CH3C6H4CHO
5i
5j
15
20
90
88
92
183–185 185–187
218–220 219–222
270–272 273–274
[44]
[46]
[43]
10
11
5k 12
12
13
2-FC6H4CHO
C6H5CHO
5l
15
96
93
286–288 New
–
6a 20
200–202 201–203
[47]
14
4-ClC6H4CHO
6b 15
95
205–207 208–210
[47]
1 3

Journal of the Iranian Chemical Society
Table 2 (continued)
Refe
renc
es
M.P. ( C)
Reported
Time
Yield
Entry Aldehyde
Product
(min.) (%)a
Found
15
16
2-ClC6H4CHO
6c 18
91
94
187–189 188–190
204–206 211–213
[47]
[47]
4-BrC6H4CHO
6d 10
17
18
19
4-NO2C6H4CHO
2-NO2C6H4CHO
4-ClC6H4CHO
6e 20
92
90
92
188–190 186–188
220–222 218–220
188–190 195–197
[47]
[47]
[48]
6f
20
6g 23
20
21
2-ClC6H4CHO
C6H5CHO
6h 30
89
88
146–148 144–146
191–193 195–196
[48]
[48]
6i
25
1 3

Journal of the Iranian Chemical Society
Table 2 (continued)
Refe
renc
es
M.P. ( C)
Reported
Time
Yield
Entry Aldehyde
Product
(min.) (%)a
Found
22
23
4-BrC6H4CHO
4-FC6H4CHO
6j
20
93
90
200–202 199–201
197–199 195–196
[48]
[48]
6k 35
24
4-OCH3C6H4CHO
6l
35
30
88
89
170–172 171–173
[48]
[48]
6
m
25
3-NO2C6H4CHO
198–200 197–198
aIsolated yields
120 °C (Scheme 2). As shown in Table 1, for both of the
reactions, a trace amount of the product is obtained when
the reactions were proceeded in the absence of the catalyst.
After optimization of the reactions conditions and to
improve these protocols, different types of aromatic alde-
hydes with electron-donating and electron-withdrawing
functional groups were used for the synthesis of 3-amino-
1-aryl-1H-benzo[f] chromene-2-carbonitrile, 1-(benzothia-
zolylamino)phenylmethyl-2-naphthol, and 1-(benzoimida-
zolylamino)phenylmethyl-2-naphthol derivatives under the
optimized conditions. As represented in Table 2, various
aldehydes with both electron-donating and electron-with-
drawing substituents are converted to the corresponding
products in short times and good-to-excellent yields.
Results and discussion
At the first step and to achieve the optimum reaction con-
ditions, the synthesis of 3-amino-1-(4-chlorophenyl)-1H-
benzo[f] chromene-2-carbonitrile (5b) and 1-benzothia-
zolylamino-(4-chlorophenylmethyl)-2-naphthol (6b) was
selected as two model reactions in various conditions such
as different amounts of the catalyst [[H2-DABCO][HSO4]2],
and various solvents and temperatures. The results are sum-
marized in Table 1. As it is clear from this table, the best
yield and time for the synthesis of the compound 5b can
be resulted in the presence of 0.030 g of the catalyst, in the
absence of solvent at 100 °C, while, in the case of the com-
pound 6b, the best results can be obtained in the presence
of 0.030 g of the catalyst, under solvent-free conditions at
1 3

Journal of the Iranian Chemical Society
Table 3 Compared performance of various catalysts with [H2-DABCO][HSO4]2 in the synthesis of 3-amino-1-aryl-1H-benzo[f]chromene-2-car-
bonitrile [entries 1–9] and 1-(benzothiazolylamino)phenylmethyl-2-naphthol [entries 10–16] derivatives of 4-chlorobenzaldehyde
Entry Catalyst
Amount (mol%) Conditions
Time (min.) Yield (%) TON
TOF (min −1
)
References
1
2
3
4
5
6
7
8
9
Morpholine
30
5
0.030 g
0.01
0.01
30
H2O/r.t
H2O/reflux
H2O/reflux
Solvent-free/125 °C
CH3CN/reflux
C2H5OH/r. t
H2O/reflux
CH3CN/reflux
Solvent-free/100 °C
180
80
240
60
240
120
20
240
5
87
85
91
100
85
72
92
91
96
90
290
17
–
1.61
21.25
–
16666.67
3541.67
0.02
[28]
[46]
[27]
[49]
[50]
[51]
[52]
[53]
CuSO4·5H2O
H14[NaP5W30O110
Na2CO3
Fe(HSO4)3
DABCO
Nanozeolite CP
Methanesulfonic acid 0.1
[H2-DABCO][HSO4]2 0.0097
HPA
]
1×106
85×104
240
0.01 g
–
–
91×103
397.16
989690.72 197938.14
3000
This work
[54]
10
3
H2O/45 °C with
ultrasonic irradia-
tion
110
27.27
11
12
13
14
15
16
LiCl
TCCA
SDS
KOH/MgO
Oxalic acid
1.1
10
20
0.050 g
30
H2O/90 °C
Solvent-free/80 °C
H2O/100 °C
Solvent-free/70 °C
Solvent-free/80 °C
Solvent-free/120 °C
360
20
60
180
4
92
96
88
92
91
95
8363.63
960
440
23.23
48
7.33
–
[55]
[56]
[57]
[30]
[29]
This work
–
303.33
979381.44 65292.09
75.83
[H2-DABCO][HSO4]2 0.0097
15
To show the merits of our catalyst activity, in Table 3,
again. After completion of the reactions, the products
were washed with water to remove the catalyst, and
then, the filtrate was evaporated under vacuum up to
70 °C to obtain the recovered catalyst. Ultimately, the
obtained catalyst was washed with diethyl ether, and dried
and reused for the same reactions. This procedure was
repeated four times for each reaction and the products
were obtained by the recovered catalyst with the least
change in the reaction times and yields. The results are
demonstrated in Figs. 1 and 2.
the results obtained from the synthesis of 3-amino-1-
aryl-1H-benzo[f]chromene-2-carbonitriles and 1-(ben-
zothiazolylamino)phenylmethyl-2-naphthols catalyzed by
[H2-DABCO][HSO4]2 are compared with other reported
results in the literatures. As shown in this table, this
method avoids from some of disadvantages associated
with the other procedures such as low yields, long reac-
tion times, hard conditions for the catalyst preparation,
using ultrasonic irradiation, and high catalyst loading.
The proposed mechanism for these reactions is shown
in Scheme 3. According to this mechanism, at first, car-
bonyl group of the aldehyde (1) is activated in the pres-
ence of [H2-DABCO][HSO4]2. After that, the mecha-
nism is divided into two distinct routes. In route 1, this
activated carbonyl group is attacked by nucleophilic
compound (a) to give the cyanoolefin (b). In continue,
compound (b) is attacked by 2-naphthol (2) to produce
Michael-addition product. Then, after cyclization and tau-
tomerization steps, the corresponding product (5a–5l) is
produced.
Conclusion
In this study, [H2-DABCO][HSO4]2 is used as a novel
acidic ionic liquid catalyst in the promotion of multi-
component synthesis of 3-amino-1-aryl-1H-benzo[f]
chromene-2-carbonitriles, 1-(benzothiazolylamino)phe-
nylmethyl-2-naphthols and 1-(benzoimidazolylamino)
phenylmethyl-2-naphthols. The most appealing feature of
this catalyst is using accessible and inexpensive materials
to synthesize the catalyst. Besides, the presented protocols
represent some advantages such as avoiding the use of
toxic solvents, ease of preparation of the catalyst, excel-
lent yields, simple work-up, and recyclability of the cata-
lyst. Moreover, the results clearly show that this method
can tolerate a wide range of various substituted aldehydes
including electron-withdrawing or electron-donating
groups.
In route 2, the activated carbonyl group can be attacked
by 2-naphthol (2), to give compound (d). Then, compound
(d) is attacked by 2-aminobenzimidazole/2-aminobenzo-
thiazole (4) to produce compounds 6a–6m.
To investigate the recoverability of the catalyst, the
reactions of 3-amino-1-(4-chlorophenyl)-1H-benzo[f]
chromene-2-carbonitrile (5b) and 1-benzothiazolylamino-
(4-chlorophenylmethyl)-2-naphthol (6b) were studied
1 3

Journal of the Iranian Chemical Society
δ+
H
IL
from
O
O
IL
Ar
H
H
Ar
(1)
NH
C
N
OH
IL
CH
Route 2
IL
Route 1
N
N
(2)
(a)
(3)
-H
2O
Ar
CN
OH
X
OH
CN
+
NH2
Ar
N
(4)
-H
(d)
2O
IL
IL
Michael addition
CN
CN
X
H
Ar NH
OH
Ar
NH
(b)
+
(6)
OH
(2)
IL
Michael addition
Ar
O
Ar
O
Ar
O
H
H
CN
CN
NH
CN
Tautomerism
Cyclization
[from IL]
C
NH2
N
H
H
[from IL]
(5)
(c)
Scheme 3 Proposed mechanism for the one-pot synthesis of 3-amino-1-aryl-1H-benzo[f] chromene-2-carbonitrile, 1-(benzothiazolylamino)phe-
nylmethyl-2-naphthol, and 1-(benzoimidazolylamino)phenylmethyl-2-naphthol derivatives using [H2-DABCO][HSO4]2 as the catalyst
1 3

Journal of the Iranian Chemical Society
10. F. Eiden, F. Denk, Arch. Pharm. 324, 353 (1991)
96
94
100
90
80
70
60
50
40
30
20
10
0
90
11. S.O. Podunavac-Kuzmanović, D.M. Cvetković, L.S. Vojinović,
Acta Period. Technol. 35, 239 (2004)
87
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13. S.O. Podunavac-Kuzmanović, D.M. Cvetković, J. Serb. Chem.
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