Synthesis of spirochromene derivatives catalyzed by Mn(bpyo)2/MCM-41 in water

Article abstract of DOI:10.1007/s00706-014-1292-8

A three-component one-pot synthesis of spirochromene derivatives by condensing cyclic 1,3-diketones, isatin or acenaphthenequinone, and malononitrile using a catalytic amount of Mn(bpyo)₂/MCM-41 in refluxing water is reported.

Full text of DOI:10.1007/s00706-014-1292-8

Monatsh Chem
DOI 10.1007/s00706-014-1292-8
ORIGINAL PAPER
Synthesis of spirochromene derivatives catalyzed by Mn(bpyo)2/
MCM-41 in water
Mansoureh Daraie
Majid M. Heravi
•
Yahya S. Beheshtiha
•
Received: 1 March 2014 / Accepted: 5 August 2014
Ó Springer-Verlag Wien 2014
Abstract A three-component one-pot synthesis of spiro-
chromene derivatives by condensing cyclic 1,3-diketones,
isatin or acenaphthenequinone, and malononitrile using a
possess a broad spectrum of biological activities such as
antiviral [7], herbicidal [8], analgesic [9], antitumor [10],
and central nervous system activities [11].
catalytic amount of Mn(bpyo) /MCM-41 in refluxing water
2
Several methods for the synthesis of spirochromenes
have been reported. The conventional synthesis involves a
three-component condensation of cyclic 1,3-diketones,
isatin or acenaphthenequinone, and malononitrile
(Scheme 1). The syntheses included the use of microwave
is reported.
Keywords Spirochromene ꢀ Mn(bpyo) /MCM-41 ꢀ
2
Reaction in water ꢀ Multi-component one-pot reaction
[
12], ultrasonic irradiation technology [13], and catalysts
such as KAl(SO ) ꢀ12H O [14], NH Cl [15], InCl [16],
4
2
2
4
3
Introduction
L-proline [17], b-cyclodextrin [18], and sodium stearate
[
19] were reported.
Nowadays, the concept of privileged medicinal compounds
or scaffolds has appeared as one of the leading principles of
drug discovery process. Heterocyclic compounds contain-
ing a chromene scaffold form the core of some cytostatic
alkaloids and a part of pharmacophores of molecules with
various biologically active molecules [1], including spas-
molytic, anticoagulant, diuretic, anticancer, etc. [2–4].
Many biologically active structures consist of rigid hetero
ring systems such as spiro moieties. The spiro functionality
has been also characterized by highly pronounced phyto-
chemicals properties in both alkaloids and terpenoids [5].
Consequently, spiro-chromene, -pyran and -pyrazole cycles
with distinct orientations for target recognition have
attracted great interest in synthetic chemistry [6]. The
functionalized chromene and spirochromene moieties
Recently, a great attention has been focused on the use
of water as a green solvent in various organic transfor-
mations. In addition to its abundance and economical and
safety reasons, water has naturally become as a substitute
and an alternative environmentally benign solvent in
organic synthesis [20–22]. The use of aqueous medium as
solvent also reduces the harmful effects of organic solvents
on the environment.
Mesostructured materials have attracted a lot of con-
sideration on for the design of catalysts. MCM-41, due to
high surface area and thermal stability, is one of the sig-
nificant mesoporous molecular sieves [23]. In the last
decade, Mn complexes were widely used as homogeneous
catalysts in oxidation reactions [24, 25]. Heterogenization
of Mn complexes has been achieved with e.g. polymers
[
26], zeolites [27], and mesoporous silica [28, 29].
Recently, Mn-MCM-41 was applied as catalyst [30] in
various reactions such as hydroxilation of benzene [31],
oxidation of ethylbenzene to acetophenone [32], and oxi-
dation of cyclohexene to cyclohexenol and cyclohexenone
Electronic supplementary material The online version of this
article (doi:10.1007/s00706-014-1292-8) contains supplementary
material, which is available to authorized users.
M. Daraie ꢀ Y. S. Beheshtiha ꢀ M. M. Heravi (&)
Department of Chemistry, School of Sciences, Alzahra
University, Vanak, Tehran, Iran
[
33]. We have reported the synthesis and catalytic activity
0
0
of Mn(II) complex with 2,2 -bipyridine 1,1 -dioxide ligand
within nanoreactors of MCM-41 [34].
e-mail: mmh1331@yahoo.com
123

M. Daraie et al.
Scheme 1
O
NH2
CN
Mn-MCM-41
+
+
X
X
CN
CN
N
H
O
H O/reflux
O
O
2
N
H
O
O
O
O
NH2
CN
Mn-MCM-41
+
+
H O/reflux
2
Table 1 Optimization of the reaction conditions for the synthesis of
spirochromene compounds under reflux
It is noteworthy to mention that the catalyst is recyclable
and could be reused without significant loss of activity. The
catalyst has been recovered and reused for four times in the
model reaction in aqueous media and the obtained results
are summarized in Table 3.
a
Entry
Catalyst
Time/min
Yield/%
1
2
3
4
5
a
H
5
PMo10
V
2
O
40
65
75
85
50
6
70
70
60
65
96
SSA
In summary, we report here a high yielding one-pot
synthesis of spirochromene derivatives from the conden-
Hexamethylene tetramine
Sulfamic acid
sation
of
cyclic
1,3-diketones,
isatin
or
Mn(bpyo)
Isolated yield
2
/MCM-41
acenaphthenequinone, and malononitrile using a catalytic
amount of Mn(bpyo) /MCM-41 under simple and conve-
2
nient conditions. The conditions are mild and a wide range
of functional groups can be tolerated. Using Mn(bpyo)2/
MCM-41 as catalyst offers advantages including simplicity
of operation, reusability, easy work-up, and high yields of
products. This work will not only lead to a practical syn-
thetic method but also expand the versatility of clean
organic reactions in water.
As a part of our ongoing efforts in search of synthetic
approaches for the preparation of organic compounds with
potential biological applications under eco-friendly condi-
tions [35–38], we wish to report the use of Mn-MCM-41 as
an efficient, green, and reusable catalyst for three-compo-
nent one-pot synthesis of spirochromene systems, by
condensing of cyclic 1,3-diketones, isatin or acenaphthen-
equinone, and malononitrile using a catalytic amount of
Mn-MCM-41 in refluxing water.
Experimental
Melting points were measured by using the capillary tube
method with an Electrothermal 9200 apparatus. NMR
spectra were recorded on a Bruker AQS 500-AVANCE
spectrometer at 400 MHz, respectively, using TMS as an
internal standard (DMSO solution). IR spectra were recor-
ded from KBr disks on the FT-IR Bruker Tensor 27. The
reactions were monitored by TLC. All solvents and reagents
were purchased from Aldrich and Merck with high-grade
quality, and used without any purification. All products
were characterized by their spectra and physical data.
Results and discussion
In initial studies, we studied the condensation of dimedone,
isatin, and malononitrile as a model reaction in the presence
of a variety of catalysts, to establish the possibility of our
strategy to spirochromene compounds and to optimize the
reaction conditions. As shown in Table 1, the best results
were obtained using Mn(bpyo) /MCM-41 (0.04 g).
2
To establish the scope of this novel methodology, we
tested a variety of 1,3-cyclic diketones under the optimized
reaction conditions and the obtained results are summarized
in Table 2. All the reactions delivered excellent product
yields. In all cases, the product was isolated by filtration and
recrystalization from ethanol to separate the catalyst.
General procedure
Asolutionofacyclic1,3-diketones(1 mmol), malononitrileor
ethylcyanoacetate (1 mmol), isatin or acenaphthenequinone
1
23

Synthesis of spirochromene derivatives
2
Table 2 Synthesis of spirochromene derivatives in refluxing water using a catalytic amount of Mn(bpyo) /MCM-41
a
Entry
Product
Time/min
Yield/%
M.p./°C
Obs.
Lit.
1
10
95
296–298
252–253
292–294
298–299 [17]
O
O
NH2
CN
N
O
H
2
18
92
253–255 [17]
O
O
O
O
NH2
CO Et
2
N
H
O
3
6
96
290–292 [17]
O
NH2
CN
N
H
O
4
12
93
254–256
256–258 [17]
O
NH2
CO Et
2
N
H
O
5
14
94
298–299
[300 [17]
O
O
O
NH2
CN
N
H
O
6
20
89
254–256
251–253 [17]
O
O
O
NH2
CO Et
2
N
H
O
123

M. Daraie et al.
Table 2 continued
a
Entry
Product
Time/min
20
Yield/%
91
M.p./°C
Obs.
Lit.
7
8
9
241–242
260–263
272–274
240–242 [38]
H N
2
O
NC
N
O
H
27
88
262–264 [38]
H N
2
O
EtO C
2
N
H
O
22
90
273–275 [40]
O
NH
HN
O
O
NH2
CN
N
O
H
1
0
28
86
208–210
207–209 [40]
O
NH
HN
O
O
NH2
CO Et
2
N
H
O
1
1
1
1
2
3
18
24
20
92
89
93
235–237
233–234
284–285
236–237 [17]
235–236 [17]
285–286 [41]
Ph
N
N
O
NH2
CN
N
H
O
Ph
N
N
O
NH2
CO Et
2
N
H
O
NH
N
O
NH2
CN
N
H
O
1
23

Synthesis of spirochromene derivatives
Table 2 continued
a
Entry
Product
Time/min
20
Yield/%
90
M.p./°C
Obs.
Lit.
14
15
16
281–284
240–241
245–246
280–281 [41]
NH
N
O
Ph
Ph
O
NH2
CN
N
H
O
25
87
242–243 [41]
NH
N
O
NH2
CO Et
2
N
H
O
15
90
245–247 [43]
O
O
NH2
CN
1
1
1
7
8
9
10
15
17
94
90
92
267–269
258–260
[300
268–270 [42]
259–262 [42]
[300 [42]
O
O
O
NH2
CN
O
O
O
NH2
2
CO Et
O
O
O
O
NH2
CN
123

M. Daraie et al.
Table 2 continued
a
Entry
Product
Time/min
22
Yield/%
89
M.p./°C
Obs.
Lit.
2
0
193–195
194–196 [43]
O
O
O
O
NH2
CO Et
2
2
1
25
93
[300
[300 [42]
H N
2
O
NC
O
2
2
25
92
[300
[300 [42]
O
HN
NH
O
O
O
NH2
CN
2
3
28
87
256–258
258–260 [43]
O
HN
NH
O
O
O
NH2
CO Et
2
2
4
20
91
194–196
193–196 [43]
Ph
N
N
O
O
NH2
CN
2
5
22
92
296–297
298–299 [42]
NH
N
O
O
NH2
CN
1
23

Synthesis of spirochromene derivatives
Table 2 continued
a
Entry
Product
Time/min
28
Yield/%
89
M.p./°C
Obs.
Lit.
2
6
246–248
247–248 [42]
NH
N
O
O
NH2
CO Et
2
a
Isolated yield
6
7
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Time/min
Yield/%
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completion of the reaction which was monitored by TLC, the
mixture was cooled to room temperature. The mixture was
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Acknowledgments S. Y. Sh. Beheshtiha, is thankful from Alzahra
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