Basic ionic liquid-catalyzed one-pot synthesis of the spiroacenaphthylene derivatives in water medium

Article abstract of DOI:10.1016/j.mencom.2012.05.012

The basic ionic liquid (benzyl)(dimethyl)(N,N-dimethylaminoethyl)ammonium chloride was found to be an efficient and reusable catalyst for the synthesis of spiroacenaphthylenes via the multicomponent reaction between acenaphthenequinone, malononitrile and

Full text of DOI:10.1016/j.mencom.2012.05.012

Mendeleev
Communications
Mendeleev Commun., 2012, 22, 148–149
Basic ionic liquid-catalyzed one-pot synthesis
of the spiroacenaphthylene derivatives in water medium
Jia Zheng and Yiqun Li*
Department of Chemistry, Jinan University, Guangzhou 510632, P. R. China. Fax: +86 20 8522 8537;
e-mail: tlyq@jnu.edu.cn
DOI: 10.1016/j.mencom.2012.05.012
The basic ionic liquid (benzyl)(dimethyl)(N,N-dimethylaminoethyl)ammonium chloride was found to be an efficient and reusable
catalyst for the synthesis of spiroacenaphthylenes via the multicomponent reaction between acenaphthenequinone, malononitrile and
a-methylenecarbonyl compounds (β-diketones, pyrazolones) in water.
Since the global attention for environmental protection increasing
during the last decades, more and more green chemical processes
O
O
with less pollution have been developed. As a green reaction
media, water could strongly enhance the rate of many organic
reactions due to its hydrophobic effects.1 Organic reactions in
water without using harmful organic solvents have being focused
on and many multicomponent reactions have been reported.2
As an important class of naturally occurring substances, spiro
compounds were characterized by highly pronounced biological
properties.3 On the other hand, heterocyclic compounds con-
taining pyran ring also possess a wide spectrum of biological
activities such as spasmolytic, anticoagulant, diuretic, anticancer,
etc.4 Syntheses of spiro heterocycles, including the use of micro-
wave,5 ultrasonic irradiation technology,6 and catalysts such as
KAl(SO4)2·12H2O,7 NH4Cl,8 InCl3,9 l-proline,10 β-cyclodextrin,11
sodium stearate,12 etc., were reported. But, to the best of our
knowledge, there are just a few reports on the synthesis of spiro-
acenaphthylenes catalyzed by Et3N.13
Due to the biological activities of spiro compounds contain-
ing pyran moieties, we take interest in developing an environ-
mentally benign approach for synthesis of spiroacenaphthylene
derivatives. As efficient catalyst and solvent, ionic liquids play
an increasingly key role in organic reactions.14 Recently, we
reported (benzyl)(N,N-dimethylaminoethyl)dimethylammonium
chloride {[BDDMA]Cl, Me2N+(Bn)(CH2)2NMe2Cl−} as an effi-
cient, fast, and convenient catalyst for the synthesis of 2-amino-
2-chromenes under solvent-free conditions.15 Some other basic
ionic liquids were successfully used in three-component pyran
assembling.16
Herein, we found that basic ionic liquid [BDDMA]Cl could
also efficiently promote the one-pot three-component condensa-
tion between acenaphthenequinone, malononitrile and various
a-methylenecarbonyl compounds, especially pyrazolones, in water.
Moreover, several novel spiroacenaphthylene derivatives contain-
ing pyrazole ring were prepared successfully by this protocol
(Scheme 1).†
Initially, we used acenaphthenequinone 1, malononitrile 2 and
4-hydroxycoumarin 3c as model reaction to explore the influence
of temperature and the amount of catalyst on the reaction outcome
(Table 1, entries 1–10). We just only obtained the Knoevenagel
condensation product when the reaction was carried out at room
temperature with (Table 1, entry 1) or in the absence of catalyst
(entry 6). As shown in Table 1, the best result was achieved when
O
CN
CN
CN
2
[BDDMA]Cl
H2O
O
O
NH2
1
3a–l
4a–l
O
O
OH
Me
O
N
Me
Pr
NH
3d
O
O
O
O
Me
N
3a
3c
3b
Me
Ph
Ph
O
O
O
O
N
N
N
N
N
Me
NH
NH
Me
3e
3f
3g
3h
Me
O
Ph
O
O
N
N
N
N
Ph
Me
O
N
N
N
Ph
N
Ph
Cl
Cl
3j
3k
Scheme 1
Typical procedure for the synthesis of 2'-amino-7',7'-dimethyl-2,5'-dioxo-
3l
3i
†
5',6',7',8'-tetrahydro-2H-spiro[acenaphthylene-1,4'-chromene]-3'-carbo-
nitrile 4a. An equimolar (1.0 mmol) mixture of acenaphthenequinone 1,
malononitrile 2, dimedone 3a and ionic liquid (15.0 mol%) in 5.0 ml
water was stirred at 80°C for the specified time (Table 2). Upon comple-
tion (monitored by TLC), the solid was filtered off and washed with water
(2×5 ml) and cold ethanol (2×2 ml) to obtain sufficiently pure product
(TLC pure). The thus obtained material was further purified by recrys-
tallization from ethanol or ethanol–acetone. The catalyst contained in the
filtrate can be used in next run without further purification.
1
4a: yellow solid, mp 256–257°C. H NMR (300 MHz, DMSO-d6) d:
1.03 (s, 3H, Me), 1.04 (s, 3H, Me), 2.08 (q, 2H, CH2, J 36.0 Hz), 2.63 (s,
2H, CH2), 7.34 (s, 2H, NH2), 7.39–8.28 (m, 6H, HAr). IR (KBr, n/cm–1):
3369, 3293, 3245, 3182, 2954, 2193, 1717, 1665, 1600, 1347.
For characteristics of compounds 4b–l, see Online Supplementary
Materials.
the reaction was performed with 15 mol% of catalyst at 80°C
.
Under the optimized reaction conditions, a series of spiro-
acenaphthylene derivatives 4a–l was successfully synthesized
© 2012 Mendeleev Communications. All rights reserved.
– 148 –

Mendeleev Commun., 2012, 22, 148–149
Table 3 Catalytic systems for synthesis of 4c.
Catalyst (mol%) Solvent T/°C Time/h Yield (%) Reference
Table 1 Optimization of reaction conditions.a
Entry
Cat. (mol%)
T/°C
Time/h
Yield (%)b
1
2
3
4
5
6
7
8
9
10
10
10
10
10
0
25
45
60
80
100
80
80
80
80
80
5
5
3
2
2
5
5
1.5
1.5
1.5
Knoevenagel product
Incomplete
89
90
Alum (10)
Alum (10)
Et3N (200)
EtOH–H2O 60
EtOH–H2O 25
EtOH reflux
80
5
24
4
63
53
60
90
7
7
13(a)
This work
[BDDMA]Cl (15) H2O
1.5
89
Knoevenagel product
5
85
90
87
88
This work was supported by the National Natural Science
Foundation of China (grant nos. 21072077 and 20672046)
and the Guangdong Natural Science Foundation (grant nos.
10151063201000051 and 8151063201000016).
15
20
25
10
a The reaction was carried out with acenaphthenequinone 1 (1 mmol), malono-
nitrile 2 (1 mmol), 4-hydroxycoumarin 3c (1 mmol) and [BDDMA]Cl as
catalyst in water (5 ml). b Isolated yield of 4c.
Online Supplementary Materials
Supplementary data associated with this article can be found
in the online version at doi:10.1016/j.mencom.2012.05.012.
Table 2 Synthesis of spiroacenaphthylene derivatives 4.a
References
Entry Compound 3 Product Time/h Yield (%)b Mp/°C
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2
3
4
5
6
7
8
9
3a
3b
3c
3d
3e
3f
3g
3h
3i
4a
4b
4c
4d
4e
4f
4g
4h
4i
1
1
1.5
1
2
2
3
2
2
89
80
90
89
75
77
66
92
75
92
79
71
256–2578
242–2448
>300
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183–186
264–266
159–161
215–217
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3j
3k
3l
4j
4k
4l
2
3
4
a Reaction conditions: acenaphthenequinone 1 (1 mmol), malononitrile 2
(1 mmol), a-methylenecarbonyl compounds 3 (1 mmol), [BDDMA]Cl
(15 mol%) as catalyst, water (5 ml), 80°C. b Isolated yield.
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(Table 2). Reactions with various substrates 3 including 1,3-di-
ketones and pyrazolones proceeded smoothly to furnish the cor-
responding products 4. All the substrates afford good to excellent
yields in short time, and among the products, compounds 4e–j,l
are new spiroacenaphthylene derivatives.
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K. R. Rao, Can. J. Chem., 2009, 87, 1704.
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Chem. Rev., 2010, 79, 543).
Then we chose the reaction of acenaphthenequinone 1,
malononitrile 2 and 4-hydroxycoumarin 3c to further examine
the reusabilities of [BDDMA]Cl. After filtering, the catalyst con-
tained in the filtrate could be directly used in the subsequent run
without further treatment under the mentioned conditions. The
yield of product 4c was 89, 90, 90, 89 and 88% in consecutive
1 to 5 runs, respectively, which indicated that the catalyst could
be reused for at least 5 runs without loss of the activities.
To show the advantage of this work in comparison with
previously described procedures, we took synthesis of 4c for
a representative example. As shown in Table 3, in comparison
with reported protocols, our catalytic system has merits of higher
yield, shorter time, without using organic solvent as co-solvent,
and efficient reusablilites.
15 L. Chen, X. J. Huang, Y. Q. Li, M. Y Zhou and W. J. Zheng, Monatsh.
Chem., 2009, 140, 45.
16 J. Zheng and Y. Li, Mendeleev Commun., 2011, 21, 280.
In conclusion, we have developed a practical and efficient
one-pot synthesis of various spiroacenaphthylene derivatives in
water with a reusable basic ionic liquid as the catalyst. This
method offers the advantages of environmental compatibility,
mild reaction conditions, short reaction times, high yields and
operational simplicity.
Received: 23rd November 2011; Com. 11/3839
– 149 –