A synthesis of spirofuran-indenoquinoxalines via isocyanid-based one-pot four-component reaction

Article abstract of DOI:10.1016/j.cclet.2016.03.015

A simple and versatile procedure for the combinatorial synthesis of (Z)-dialkyl-5-(alkylimino)-5H-spiro[furan-2,11′-indeno[1,2-b]quinoxaline]-3,4-dicarboxylates via the catalyst-free one-pot four-component reaction of ninhydrin, benzene-1,2-diamines, dial

Full text of DOI:10.1016/j.cclet.2016.03.015

Accepted Manuscript
Title: A synthesis of spirofuran-indenoquinoxalines via
isocyanid-based one-pot four-component reaction
Author: Nahid Sabouri Gholam Hossein Mahdavinia Behrouz
Notash
PII:
S1001-8417(16)30044-4
DOI:
Reference:
http://dx.doi.org/doi:10.1016/j.cclet.2016.03.015
CCLET 3634
To appear in:
Chinese Chemical Letters
Received date:
Revised date:
Accepted date:
27-11-2015
18-1-2016
18-2-2016
Please cite this article as: N. Sabouri, G.H. Mahdavinia, B. Notash, A synthesis of
spirofuran-indenoquinoxalines via isocyanid-based one-pot four-component reaction,
Chinese Chemical Letters (2016), http://dx.doi.org/10.1016/j.cclet.2016.03.015
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Graphical Abstract
A synthesis of spirofuran-indenoquinoxalines via isocyanid-based one-pot four-component reaction
a
a1
b
Nahid Sabouri , Gholam Hossein Mahdavinia , Behrouz Notash
a
Department of Chemistry, Marvdasht Branch, Islamic Azad University, Marvdasht, Iran
Chemistry Department, Shahid Beheshti University, G. C., Evin, Tehran 1983963113, Iran
b
A synthesis of (Z)-dialkyl-5-(alkylimino)-5H-spiro[furan-2,11'-indeno[1,2-b]quinoxaline]-3,4- dicarboxylates via one-pot four-component
reaction is described.
—
——
1
Corresponding author.
E-mail address: hmahdavinia@gmail.com.
Page 1 of 6

Original article
A synthesis of spirofuran-indenoquinoxalines via isocyanid-based one-pot four-
component reaction
Nahid Sabouri , Gholam Hossein Mahdavinia a, ∗, Behrouz Notash b
a
a
Department of Chemistry Marvdasht Branch, Islamic Azad University, Marvdasht, Iran.
Departmen Chemistry, Shahid Beheshti University, G. C., Evin, Tehran 1983963113, Iran.
b
ARTICLE INFO
ABSTRACT
Article history:
A simple and versatile procedure for the combinatorial synthesis of (Z)-dialkyl-5-
Received 27 November 2015
Received in revised form 18 January 2016
Accepted 18 February 2016
Available online
(alkylimino)-5H-spiro[furan-2,11'-indeno[1,2-b]quinoxaline]-3,4-dicarboxylates
catalyst-free one-pot four-component reaction of ninhydrin, benzene-1,2-diamines, dialkyl
acetylenedicarboxylates and isocyanides is described.
via
the
Keywords:
One-pot
Multicomponent
Catalyst free
Spirofuranindenoquinoxalines
Isocyanide
1
. Introduction
Multicomponent reactions (MCRs), particularly one-pot processes, are of current interest to organic chemists because of being
rapid, their convergence, productivity, facile execution [1] cost-effectiveness such as atom economy [2] and lower the costs of reagents
and solvents [3], protection-deprotection steps, less tedious work-up and purification [4]. Multicomponent reactions provide unmatched
opportunities for the expeditious increase of complexity and diversity in synthetic outcomes. Isocyanide-based multicomponent
reactions (IMCRs) have emerged as an efficient and powerful tool in synthetic organic chemistry [5]. One class of these reactions is the
generation of zwitterionic intermediates with the nucleophilic addition of isocyanides to activate acetylene [6].
Compounds containing furan rings are extensively found in many biologically active natural products. They are used in preparation
of many pharmaceutical products such as ascorbic acid [7], ranitidine [8], phomactin A [9], azimilide [10], dantrolene [11],
nitrofurazone [12], perillene [13], teubrevin G and teulepicin [14]. Moreover, in commerce and business, furans are important
intermediates in the preparation of dyes, essential oils, agrochemical bioregulators, cosmetics and photosensitizers [15, 16].
Much attention has been devoted to a large variety of nitrogen-containing heterocyclics and heterocyclic quinoxalines because of
their pharmacological properties and clinical applications [17]. The quinoxaline derivatives are an important group of aza-polycyclics
[
18], while indenoquinoxaline derivatives are important classes of N-heterocycles since both are useful intermediates for spiroindeno
synthesis. The main structure of many spiro compounds exhibit valuable (advantageous) pharmacological properties such anti-tumor
agents [19, 20], anti-cancer [21], natural alkaloids [22], and also biological properties like anti-bacterial, anti-microbial [23], with an
inhibitor growth factor receptor [24] of particular interest. Spiroheterocycles are also of considerable interest because the presence of a
spirocarbon provides a strengthening of the structure [22, 25] and together with a variety of furanes are the main important core of
many pharmacological agents [15].
Existing furan and quinoxaline moieties in one spiro molecule can be attractive to organic and biological chemists due to the
incorporation of more than one heterocyclic scaffold in one structure causes interesting biological properties. We therefore sought to
MW irradiation in good yields [26].
In continuation of this work, develop a simple and versatile procedure for the combinatorial synthesis of a spiro-substituted furan-
indenoquinoxaline library for biological screening.
In 2004 Azizan, et al., reported the synthesis of spirofuran-indenoquinoxalines via a three-component condensation reaction in DMF
using herein, we report a one-pot, four-component procedure for synthesis of (Z)-dialkyl-5-(alkylimino)-5H-spiro[furan-2,11'-
———
∗
Corresponding author.
E-mail address: hmahdavinia@gmail.com
Page 2 of 6

indeno[1,2-b]quinoxaline]-3,4-dicarboxylates in excellent yields, via four component reaction ninhydrin, benzene-1,2-diamines, and
zwitterionic made up of dialkylacetylenedicarboxylates and alkylisocyanide in the CH Cl at room temperature (Scheme 1).
2
2
2
. Experimental
Melting points and IR spectra of all compounds were measured with an Electrothermal 9200 apparatus and a Perkin–Elmer 783
1
13
FTIR spectrometer, respectively. Also, the H NMR and C NMR spectrum were recorded on a Bruker Avance DPX-250 instrument
using CDCl and DMSO-d as internal standard at 250 and 62.5 MHz, respectively. All of the compounds were purchased from Fluka,
3
6
Merck, and Aldrich companies, and used without further purification.
Scheme 1. Preparation of spirofuran-indenoquinoxalines derivatives.
.1. General procedure for the preparation of compounds 5:
2
Ninhydrin 1 (1 mmol), benzene-1,2-diamine 2 (1 mmol) were added at r.t. to CH Cl (10 mL) while stirring. After ca. 10 min, the
2
2
appropriate acetylenedicarboxylate 3 (1 mmol) in dichloromethane (5 mL) and the appropriate isocyanide 4 (1 mmol) in
dichloromethane (5 mL) simultaneously were added dropwise over 20 min and the reaction mixture was stirred for 8 h. After
completion of the reaction, the solvent was removed under vacuum and the product 5 was crystallized out from an EtOH-H O and
2
washed with Et O (4 mL×2) to give a white crystalline solid.
2
(
Z)-Dimethyl-5-(tert-butylimino)-5H-spiro[furan-2,11'-indeno[1,2-b]quinoxaline]-3,4-dicarboxylate (5a): White crystal, mp: 277-
1
2
7
3
1
79 °C; IR (KBr): vmax 1750, 1725, 1685; H NMR (250 MHz, CDCl ): δ 1.56 (s, 9H, 3Me), 3.39 (s, 3H, OMe), 3.96 (s, 3H, OMe),
.44-7.48 (m, 1H, Ar ), 7.50-7.64 (m, 3H, Ar), 7.66-7.79 (m, 3H, Ar), 8.12-8-20 (m, 1H, Ar); C NMR (62.5 MHz, CDCl ): δ 30.70,
3
1
3
3
1.40, 54.09, 54.30, 61.12, 112.24, 113.31, 124.55, 126.87, 130.59, 130.98, 131.13, 132.22, 132.74, 133.24, 139.62, 141.92, 142.39,
44.44, 154.17, 157.32, 162.05.
(
Z)-Dimethyl-5-(cyclohexylimino)-5H-spiro[furan-2,11'-indeno[1,2-b]quinoxaline]-3,4-dicarboxylate (5b): White crystal; mp 233-
1
2
1
35 °C; IR (KBr): vmax 1751, 1728, 1681, 1439; H NMR (250 MHz, DMSO-d ): δ 1.18-1.89 (m, 10H, 5CH of cyclohexyl), 4.09 (q,
6
2
H, J=18.5 Hz, CH-N of cyclohexyl), 3.31 (s, 3H, OMe), 3.91 (s, 3H, OMe), 7.53-7.56 (m, 1H, Ar ), 7.65-7.77 (m, 3H, Ar), 7.80-7-95
1
3
(
m, 3H, Ar), 8.16-8-21 (m, 1H, Ar); C NMR (62.5 MHz, DMSO-d ): δ 23.67, 25.20, 32.21, 32.31, 33.12, 38.13, 52.96, 53.24, 64.16,
6
8
8.12, 119.71, 123.34, 125.67, 125.94, 129.40, , 130.05, 131.4, 131.61, 133.00, 137.06, 141.16, 141.5, 143.12, 162.22, 166.19.
(
Z)-Diethyl-5-(cyclohexylimino)-5H-spiro[furan-2,11'-indeno[1,2-b]quinoxaline]-3,4-dicarboxylate (5c): White crystal; mp 220-222
1
°
C; IR (KBr): νmax 2940, 1743, 1720, 1685, 1651; H NMR (250 MHz, CDCl ): δ 0.84 (m, 3H, Me), 1.45 (m, 3H, Me), 1.20-1.82 (m,
3
0H, 5CH of cyclohexyl), 3.61 (m, 1H, CH-N of cyclohexyl), 3.85 (dq, 2H, J=15.7 Hz, J= 6.5 Hz, OCH ), 4.51 (m, 2H, OCH ),
2 2 2
.28-8.23 (m, 8H, Arom.); C NMR (62.5 MHz, CDCl ): δ 13.78, 14.53, 25.07, 25.16, 2609, 33.58, 33.63, 57.14, 62.08, 62.95, 90.26,
23.15, 124.91, 129.65, 129.80, 130.45, 130.96, 131.86, 132.62, 138.36, 139.27, 142.12, 142.14, 143.36, 143.42, 154.46, 155.14,
57.68, 159.88, 162.16.
2
3
1
7
1
1
1
3
3
(
Z)-Dimethyl-5-(tert-butylimino)-8'-methyl-5H-spiro[furan-2,11'-indeno[1,2-b]quinoxaline]-3,4-dicarboxylate (5d): White crystal;
1
mp 222-225 °C; IR (KBr): νmax 1752, 1731, 1666, 1649; H NMR (250 MHz, CDCl ): δ 1.25 (s, 9H, 3Me), 2.53 (s, 3H, Me), 3.44 (s,
H, OMe), 4.03 (s, 3H, OMe), 7.49-8.20 (m, 7H, Ar.); C NMR (62.5 MHz, CDCl ): δ 29.95, 33.64, 53.15, 53.64, 55.68, 90.76,
23.24, 124.72, 129.66, 129.78, 130.47, 130.96, 131.86, 132.62, 138.30, 140.60, 141.02, 142.17, 143.29, 143.44, 153.06, 154.37,
57.58, 160.48, 162.86.
3
1
3
3
1
1
3
(
Z)-Dimethyl-5-(cyclohexylimino)-8'-methyl-5H-spiro[furan-2,11'-indeno[1,2-b]quinoxaline]-3,4-dicarboxylate (5e): White crystal;
1
mp 237-238 °C; IR (KBr): νmax 1752, 1729, 1675, 1646; H NMR (250 MHz, CDCl ): δ 1.18-1.84 (m, 10H, 5CH of cyclohexyl), 2.51
s, 3H, Me), 3.44 (s, 3H, OMe), 3.59 (m, 1H, CH-N of cyclohexyl), 4.03 (s, 3H, OMe), 7.38-8.25 (m, 7H, Ar); C NMR (62.9 MHz,
3
2
1
3
(
CDCl ): δ 20.65, 20.84, 25.12, 26.06, 33.57, 53.11, 53.70, 57.24, 90.78, 122.96, 124.74, 128.95, 129.66, 131.84, 132.18, 138.65,
3
1
39.13, 140.35, 140.98, 141.56, 142.24, 142.33, 142.86, 153.51, 156.40, 160.45, 162.65.
Z)-Dimethyl-5-(tert-butylimino)-7',8'-dichloro-5H-spiro[furan-2,11'-indeno[1,2-b]quinoxaline]-3,4-dicarboxylate
(
(5f):
White
1
crystal; mp: 219-222 °C; IR (KBr): νmax 1758, 1764, 1671, 1653; H NMR (250 MHz, CDCl ): δ 1.35 (s, 9H, Me), 3.35 (s, 3H, OMe),
3
1
3
1
3
.84 (s, 3H, OMe), 7.17-8.22 (m, 6H, Ar); C NMR (62.9 MHz, CDCl ): δ 29.7, 52.78 53.3, 56.9, 78.49, 118.59, 123.06, 123.14,
3
24.50, 129.86, 130.57, 131.08, 131.68, 132.2, 132.81, 143.14, 153.74, 161.43, 163.64.
(
Z)-Dimethyl-7',8'-dichloro-5-(cyclohexylimino)-5H-spiro[furan-2,11'-indeno[1,2-b]quinoxaline]-3,4-dicarboxylate (5g): White
1
crystal; mp: 247-249 °C; IR (KBr): vmax 1750, 1726, 1684, 1440; H NMR (250 MHz, CDCl ): δ 1.11-1.92 (m, 10H, 5CH of
3
2
Page 3 of 6

1
3
cyclohexyl), 3.42 (s, 3H, OMe), 3.99 (s, 3H, OMe), 7.25-8.30 (m, 6H, Ar); C NMR (62.5 MHz, CDCl
3
): δ 25.6, 29.7, 33.16, 52.78
5
3.3, 56.9, 78.49, 118.59, 123.06, 123.14, 124.50, 129.86, 130.57, 131.08, 131.68, 132.2, 132.81, 143.14, 153.74.
3. Results and discussion
Recent success in conjunction with isocyanide-based, multicomponent reactions provided a means to constructing novel
heterocycles systems [15]. The polycyclic heterocycles, like indenoquinoxalines, leads to forming the rings of spiroindeno-
quinoxalines. In our initial test reaction, the three components, between 11H-indeno[1,2-b]quinoxalin-11-one 6a, tert-butyl isocyanide
4
and dimethylacetylenedicaboxylate (DMAD) 3 without any catalyst in dry CH Cl at r.t for 10 h, gave (Z)-dimethyl-5-(tert-
2 2
butylimino)-5H-spiro[furan-2,11'-indeno[1,2-b]quinoxaline]-3,4-dicarboxylate 5a in excellent yield (Scheme 2).
Scheme 2. The synthesis of spirofuran-indenoquinoxalines via a three-component condensation reaction.
To optimize the conditions, various aprotic and protic solvents were investigated at reflux and r.t. conditions. In protic solvents the
desired product was not obtained. However, the desired product was formed in aprotic solvents and was produced under the. Best the
conditions in dry CH Cl at r.t. with excellent yield. The results are summarized in Table 1.
2
2
Table 1
Optimization of conditions for the formation of spirofuran-indenoquinoxaline 5a.
Entry
Solvent
EtOH
T (°C)
Reflux
Reflux
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
Time (h)
Yield (%)
None
58
98
None
30
None
None
45
1
2
3
4
5
6
7
8
10
24
8
24
24
24
24
10
CH
CH
2
Cl
Cl
2
2
2
EtOH
THF
H
2
O
MeOH
Et
2
O
To minimize the steps required for the formation of the product and to simplify the procedure, a one-pot, four-component reaction
was planned (Scheme 1) understanding the necessity to separate intermediate 6 as well as the control of reaction time. Our studies for
this model reaction revealed that 5a could be synthesized in a one-pot reaction if 6a was prepared in situ from condensation of
ninhydrin 1 with benzene-1,2-diamine 2a at r.t. within 10 min., then treated with equimolar amounts of DMAD and tert-butyl
isocyanide within 8 h at r.t (Scheme 3). Therefore, the implication of 11H-indeno[1,2-b]quinoxalin-11-one 6a in the initial reaction is
confirmed.
Scheme 3. A synthesis of spirofuran-indenoquinoxalines via isocyanid-based one-pot four-component reaction
Having optimized the conditions, various isocyanide 4 and acetylenedicarboxylate 3 were condensed with ninhydrin 1 and benzene-
1
1
,2-diamines 2 to afford the corresponding products 5a-5g (Scheme 1). The results presented in Table 2 show that the various benzene-
,2-diamine and the methyl and ethyl acetylenedicarboxylates and isocyanides were successfully applied in this process to afford the
corresponding (Z)-dialkyl-5-(alkylimino)-5H-spiro[furan-2,11'-indeno[1,2-b]quinoxaline]-3,4-dicarboxylates in excellent yields.
Table 2
One-pot, four-component synthesis of spirofuran-indenoquinoxalines 5a–5g.
1
2
3
Entry
R
R
R
Product
Yield (%)
1
2
3
4
5
H
H
H
Me
Me
Me
Me
Et
Me
Me
t-Bu
5a
5b
5c
5d
97
98
94
98
96
Cyclohexyl
Cyclohexyl
t-Bu
Cyclohexyl
5e
Page 4 of 6

6
7
Cl
Cl
Me
Me
t-Bu
Cyclohexyl
5f
5g
86
84
The plausible mechanism for the synthesis of (Z)-dialkyl-5-(alkylimino)-5H-spiro[furan-2,11'-indeno[1,2-b]quinoxaline]-3,4-
dicarboxylate compounds 5 is shown in Scheme 4. We envisioned that this reaction could be realized in a one-pot, two-step manner.
Initially, ninhydrin 1 and the benzene-1,2-diamine 2 react to form the corresponding indenoquinoxalinone A, the zwitterionic
intermediate B, formed by the 1:1 interaction between the isocyanide and acetylenedicarboxylate, which attacks preferentially the
carbonyl group of indeno-quinoxalines 6, leading to dipolar intermediate C, and subsequently leading to ring five-membered and the
spirocyclic product 5a.
Scheme 4. Proposed mechanism for the synthesis of (Z)-dimethyl-5-(tert-butylimino)-5H-Spiro[furan-2,11'-indeno[1,2-b]quinoxaline]-3,4-
dicarboxylate.
In order to elucidate the structure of these compounds, we determined the structure of compound 5a by X-ray crystallography [27].
The ORTEP diagram of 5a is presented in Fig. 1.
Fig. 1. ORTEP diagram of 5a. Thermal ellipsoids are at 30% probability level.
4
. Conclusion
In conclusion, we have succeeded in developing a novel approach and a clean, convenient, simple and inexpensive method for the
synthesis of spiroindenoquinoxalines via a one-pot reaction. This procedure offers significant advantages because of the minimization
of labor, time, and cost. Noteworthy, our work presents a very easy and simple reaction, at r.t conditions, without any catalyst and in a
short time frame. Additionally, the products obtained can be easily isolated via crystallization.
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[
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(
(
b) H. Chen, D. Shi, Efficient one-pot synthesis of novel spirooxindole derivatives via three-component reaction in aqueous medium, J. Comb. Chem. 12
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[
[
26] J. Azizian, A.R. Karimi, A.A. Mohammadi, M.R. Mohammadizadeh, Three component synthesis of some γ-spiroiminolactones under microwave-assisted
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27] (a) X-Ray data for 5a: C26
H
23
-3
N
3
O
5
, M = 457.47, orthorhombic system, space group P2
1
2
1
2
1
, a = 11.053(2), b = 12.311(3), c = 16.914(3) Å, V= 2301.6(8)
3
-1
3
Å , Z= 4, Dcalc = 1.320 g.cm , μ(Mo-Kα)= 0.093 mm , T = 120(2) K, crystal size of 0.50 x 0.38 x 0.10 mm . The X-ray diffraction measurement was
made on a STOE IPDS-2T diffractometer with graphite monochromated Mo-Kα radiation. The structure was solved using SHELXS. The structure
refinement and data reduction was carried out with SHELXL using the X-STEP32 suite of programs. The non-hydrogen atoms were refined
2
anisotropically by full matrix least-squares on F values to final R
1
= 0.0901, wR
2
= 0.1158 and S = 1.069 with 312 parameters using 6009 independent
reflections. Hydrogen atoms were added in idealized positions. The crystallographic information file has been deposited with the Cambridge Data Centre,
CCDC 1032226; (b) X-STEP32 Version1.07b, X-ray structure evaluation package, 2000, Stoe&Cie, Darmstadt, Germany.
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