The one-step synthesis of c,d-dihydropyrano[f] chromene derivatives in under grinding as an environmentally frinendly alternative

Article abstract of DOI:10.13005/ojc/300225

1,4-diazabicyclo[2.2.2]octane (DABCO) was used as a catalyst for one-pot, three-component condensation reactions consisting of aromatic aldehydes, malononitrile and b-Naphtol under grinding at room temperature, to afford the corresponding dihydropyrano[c]

Full text of DOI:10.13005/ojc/300225

ISSN: 0970-020 X
CODEN: OJCHEG
2014, Vol. 30, No. (2):
Pg. 587-591
ORIENTAL JOURNAL OF CHEMISTRY
An International Open Free Access, Peer Reviewed Research Journal
www.orientjchem.org
The One-step Synthesis of C,D-dihydropyrano[F]
Chromene Derivatives in Under Grinding as An
Environmentally Frinendly Alternative
ABOLGHASEM SHAMELIAKANDI1*, EBRAHIM BALALI2, TALIEH MOSAVAT2,
MOHAMMAD MEHDI GHANBARI3 and ALI EAZABADI4
1Department of Chemistry, Omidiyeh Branch, Islamic Azad University, Omidiyeh, Iran.
2Department of Chemistry, Pharmaceutical Sciences Branch, Islamic Azad University, Tehran, Iran.
3Department of Chemistry, Sarvestan Branch, Islamic Azad University, Sarvestan, Iran.
4Department of Chemistry, Centeral Tehran Branch, Islamic Azad University, Tehran, Iran.
*Corresponding author E-mail: Shameli678@gmail.com
http://dx.doi.org/10.13005/ojc/300225
(Received: March 06, 2014; Accepted: April 12, 2014)
ABSTRACT
1,4-diazabicyclo[2.2.2]octane (DABCO) was used as a catalyst for one-pot, three-
component condensation reactions consisting of aromatic aldehydes, malononitrile and -Naphtol
under grinding at room temperature, to afford the corresponding dihydropyrano[c]chromenes in
high yields. This method has the advantages of a simple operation, mild reaction conditions, high
yields, by using a less toxic and low cost chemical as a catalyst.
Key words: One-step synthesis, Chromene, Environment friendly.
INTRODUCTION
In this paper we focus on the preparation
of 3-amino-1-phenyl-1H-benzo[f]chromene-2-
carbonitrile derivatives 4 (Scheme 1) in grinding
media.
There has been considerable interest in
chromenes and their benzoderivatives, not least
because of their value for a variety of industrial,
biological, and chemical synthetic uses.1 As a result,
a large number of methods have appeared
describing novel synthesis of these heterocycles.2
2-Amino-4H-benzochromenes have been of
interest because of their biological activity3 and a
few methods have been reported for their
synthesis.4
Due to the diverse biological properties of
this compound class, there is a widespread interest
in their synthesis. Compounds with an uracil moiety
antitumor, antibacterial, antihypertensive,
vasodilator, bronchiodilator, hepatoprotective,
cardiotonic, and antiallergic activities. Some of
them exhibit antimalarial, antifungal analgesics, and
herbicidal properties5-9.

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AKANDI et al., Orient. J. Chem., Vol. 30(2), 587-591 (2014)
Previous methods for the synthesis of 3- mechanism of the one-pot reaction between
amino-1-phenyl-1H-benzo[f]chromene-2- benzaldehyde derivatives, malononitrile and â-
carbonitrile have been reported in which a two- Naphtole in the presence of DABCO, a possible
component reaction between arylidene explanation is presented in Scheme 2. The higher
malononitrile with -Naphtole occurred under harsh reactivity of the iminium group is utilized to facilitate
thermal conditions. Also, a microwave-assisted one- Knoevenagel condensation between aryl aldehyde
pot three-component cyclocondensation of 1 and malononitrile 2, which proceeds via
Phenols, benzaldehyde derivatives, and alkylnitrile intermediate 5. After dehydration, olefin 6 is
in the absence or presence of triethylamine, produced. DABCO also catalyzes the generation of
Diammonium hydrogen phosphate (DAHP) has a proposed -Naphtoxide and this intermediate
been reported. These methods exhibit some adds to olefin 5 to generate 4, after proton transfer,
disadvantages such as: harsh conditions, long tautomerization andnhydrolysis of intermediate 7
reaction times, low yields, and effluent pollution.10
(Scheme 2 and table 1).
RESULTS AND DISCUSSION
The structures of compounds 4 were
1
deduced from their H NMR, 13C NMR and IR
Herein we report a simple synthesis of 3- spectral data and their molecular weight confirmed
1
amino-1-phenyl-1H-benzo[f]chromene-2- by mass spectrometry. H NMR and 13C NMR
carbonitrile as a domino Knoevenagel–Michael spectroscopy were especially useful to elucidate
condensation, catalyzed by 0.1 eq mol of DABCO the structures of products.The mass spectra of these
in aqueous media at room temperature (Scheme compounds detected the expected molecular ion
1). Although we have not yet established the signals. Selected spectroscopic data have been
Table 1: 3-amino-1-phenyl-1H-benzo[f]chromene-2-
carbonitrile 4a–g in under grinding using DABCO Yields
refer to pure isolated products characterized b y IR,
1H and 13C N MR spectroscopy and mass spectrometry
Product Ar
Time (min)
Yield
4a
4b
4c
4d
4e
4f
4g
4h
4i
3-Chloro -C6H4
10
8
10
6
14
12
12
9
89
83
91
96
92
95
85
88
92
83
4-Chloro -C6H4
4-Cyano -C6H4
2,3- diChloro -C6H3
3-hydroxy -C6H4
3-nitro -C6H4
4-trifluoro -C6H4
C6H5
4-dimethyl- amino- C6H4
4-Br- C6H4
3
9
4k
given in general procedure section. The results a green chemistry protocol. We suggest DABCO as
obtained in the reaction of a series of representative a green and effective catalyst that does not use
aldehydes with malononitrile and -Naphtole. The harmful organic solvents for these reactions.
effect of substituents on the aromatic ring did not
show special effects in terms of yields under these
reaction conditions. We have developed an easier,
practically convenient, novel, ecologically safe
EXPERIMENTAL
All of the chemical materials used in this
method for the synthesis of 3-amino-1-phenyl-1H- work were purchased from Merck and Fluka and
benzo[f]chromene-2-carbonitrile derivatives using used without further purification. Melting points were

AKANDI et al., Orient. J. Chem., Vol. 30(2), 587-591 (2014)
589
determined with an Electro thermal 9100 apparatus
and were uncorrected. IR spectra were obtained
on an ABB FT-IR (FTLA 2000) spectrometer.1HNMR
and 13C NMR spectra were recorded on a Bruker
DRX-300 AVANCE at 300 and 75MHz (respectively)
using TMS as internal standard and CDCl3 as
solvent. Mass spectra data were obtained using a
GC-MS Hewlett Packard (EI, 20 e V) instrument.
at room temperature for 3-15 min. The progress of
the reaction was monitored by thin-layer
chromatography (TLC). After completion of the
reaction, the mixture was then concentrated under
reduced pressure, and 5 ml of water/ethanol(1:1)
was added. The remaining solid was collected by
filtration. Further purification was done by
recrystallization in EtOH.
Synthesis 3-amino-1-phenyl-1H-benzo[f]
chromene- 2-carbonitrile derivatives
3-amino-1-(3-chlorophenyl)-1H-
0
benzo[f]chromene-2-carbonitrile, mp: 202–204 C.
1
A solution of aromatic aldehyde 1 (1
IR (KBr, cm-1) 3431, 3328, 2182, 1646, 1588. H
mmol), malononitrile 2 (1.2 mmol ), -Naphtole 3 (1
mmol), and 1,4-diazabicyclo[2.2.2]octane (DABCO)
(22.4 mg, 20 mol %) in under grinding was stirred
NMR (300 MHz, CDCl3, ppm) : 5.40 (s, 1H, H-4),
6.34 (brs, 2H, NH2), 7.23–7.38 (m, 5H, H-Ar), 7.44–
7.48 (m, 2H, H-Ar), 7.87–7.98 (m, 2H, H-Ar). 13C
Scheme 1: Synthesis 3-amino-1-phenyl-1H-benzo[f]
chromene-2-carbonitrile by 20% DABCO in under grinding
Scheme 2: The proposed mechanism for the synthesis of 3-amino-1-phenyl-1H-benzo[f]chromene-
2-carbonitrile in under grinding catalyzed by 1,4-diazabicyclo[2.2.2]octane (DABCO)

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AKANDI et al., Orient. J. Chem., Vol. 30(2), 587-591 (2014)
NMR (75 MHz, CDCl3, ppm)  59.08, 111.50, C20H12N2O35Cl37Cl [M+2]+. found 368.0282; calc.
115.09, 118.33, 119.49, 120.66, 120.86, 123.38, 368.0297; C20H12N2O37Cl2 [M + 4]+. found 370.0261;
123.93, 126.44, 126.48, 126.59, 127.67, 133.27, calc. 370.0267.
137.20, 143.06, 145.77, 147.60, 159.89. HR-MS (70
eV, EI): C20H13N2O35Cl [M]+. found: 332.0705; calc.
3-amino-1-(3-hydroxyphenyl)-1H-
0
332.0716; C20H13N2O37Cl [M +2]+. found: 334.0695; benzo[f]chromene-2-carbonitrile, mp: 280–282 C.
1
calc. 334.0703.
IR (KBr, cm-1) 3419, 3327, 2187, 1642, 1586. H
NMR (300 MHz, CDCl3, ppm) : 5.40 (s, 1H, H-4),
3-amino-1-(4-chlorophenyl)-1H- 6.23 (brs, 2H, NH2), 6.63–6.67 (m, 2H, H-Ar), 6.77
0
benzo[f]chromene-2-carbonitrile, mp: 206–208 C. (d, 1H, J= 7.6 Hz, H-Ar), 7.10 (t, 1H, J= 7.6 Hz, H-Ar),
IR (KBr, cm-1) 3409, 3322, 3029, 2223, 1630, 1586. 7.34 (d, 1H, J= 8.9 Hz, H-Ar), 7.40–7.49 (m, 2H, H-
1H NMR (300 MHz, CDCl3, ppm):  5.36 (s, 1H, H-4), Ar), 7.92 (t, 3H, J= 8.9 Hz, H-Ar), 8.35 (brs, 1H, OH).
7.11 (brs, 2H, NH2), 7.25 (d, 1H, J=8.4 Hz, H-Ar), 13C NMR (75 MHz, CDCl3, ppm) : 60.18, 113.82,
7.29 (d, 1H, J=8.4 Hz, H-Ar), 7.35 (d, 1H, J= 8.9 Hz, 114.10, 115.81, 116.73, 118.36, 119.44, 123.84,
H-Ar), 7.38–7.45 (m, 3H, H-Ar), 7.80 (d, 1H, J= 8.2 124.96, 126.99, 128.46, 129.47, 129.65, 130.89,
Hz, H-Ar), 7.88 (d, 1H, J= 7.8 Hz, H-Ar), 7.92 (d, 1H, 131.43, 147.12, 147.30, 157.78, 159.60. ESI:
J= 9.0 Hz, H-Ar). 13C NMR (75 MHz, CDCl3, ppm) C20H15N2O2 [M + 1]+ found 315.11280; calc.
: 61.18, 112.37, 113.48, 114.40, 116.68, 123.58, 314.1129; C20H14N2O2Na [M+Na]+ found
125.28, 127.40, 128.56, 128.63, 129.13, 129.27, 337.09475; calc. 337.09493; C40H28N4O4Na [2M
129.92, 30.08, 131.43, 131.86, 147.10, 158.34, +Na]+ found 651.20028; calc. 651.20047.
158.68.HR-MS (70 eV, EI):C20H13N2O35Cl [M]+. found:
332.0705; calc. 332.0716; C20H13N2O37Cl [M+2]+.,
found: 334.0695; calc. 334.0703.
3 - a m i n o - 1 - ( 3 - n i t r o p h e n y l ) - 1 H -
0
benzo[f]chromene-2-carbonitrile, mp: 239–241 C.
1
IR (KBr, cm-1) 3464, 3357, 2192, 1657, 1590. H
3-amino-1-(4-cyanophenyl)-1H- NMR (300 MHz, CDCl3, ppm) : 5.61 (s, 1H, H-4),
0
benzo[f]chromene-2-carbonitrile, mp: 285–287 C. 7.15 (brs, 2H, NH2), 7.38 (d, 1H, J= 8.9 Hz, H-Ar),
IR (KBr, cm-1) 3440, 3301, 2223, 2182, 1653, 1591. 7.42–7.48 (m, 2H, H-Ar), 7.57 (t, 1H, J= 7.8 Hz, H-
1H NMR (300 MHz, CDCl3, ppm) : 5.49 (s, 1H, H-4), Ar), 7.65 (m, 1H, H-Ar), 7.85 (d, 1H, J= 7.5 Hz, H-Ar),
6.41 (brs, 2H, NH2), 7.37 (d, 1H, J= 8.9 Hz, H-Ar), 7.91–7.96 (m, 2H, H-Ar), 8.00 (d, 1H, J=6.3 Hz, H-
7.44–7.49 (m, 2H, H-Ar), 7.48 (d, 2H, J= 8.9 Hz, H- Ar), 8.05 (m, 1H, H-Ar). 13C NMR (75 MHz, CDCl3,
Ar), 7.70 (d, 2H, J =7.5 Hz, H-Ar), 7.82–7.85 (m, 1H, ppm) : 57.42, 115.04, 117.32, 120.66, 121.78,
H-Ar), 7.92–7.95 (m, 1H, H-Ar), 7.98 (d, 1H, J=8.9 122.29, 123.93, 125.60, 127.85, 129.05, 130.37,
Hz, H-Ar). 13C NMR (75 MHz, CDCl3, ppm) : 58.93, 130.52, 130.89, 131.31, 134.17, 147.43, 148.33,
110.55, 114.49, 116.83, 118.28, 119.00, 123.51, 148.44, 160.44. HR-MS (70 eV, EI): C20H13N3O3 [M]+.
125.18, 127.30, 128.26, 128.66, 130.08, 130.55, found 343.0977; calc. 343.0957.
131.49, 132.66, 147.44, 150.73, 159.84. HR-MS (70
eV, EI): C21H13N3O: [M]+. found 323.1058; calc.
323.1058.
3-amino-1-(4-trifluoromethylphenyl)-1H-
0
benzo[f]chromene-2-carbonitrile, mp: 215–217 C.
1
IR (KBr, cm-1): 3470, 3358, 2193, 1739, 1576. H
3-amino-1-(2,3- dichlorophenyl)-1H- NMR (300 MHz, CDCl3, ppm) : 5.48 (s, 1H, H-4),
benzo[f]chromene -2-carbonitrile, mp: 319–322 0C. 6.37 (brs, 2H, NH2), 7.37 (d, 1H, J=8.9 Hz, H-Ar),
1
IR (KBr, cm-1) 3439, 3322, 2135, 1630, 1589. H 7.41–7.50 (m, 4H, H-Ar), 7.64 (d, 2H, J= 8.2 Hz, H-
NMR (300 MHz, CDCl3, ppm) ä: 5.94 (s, 1H, H-4), Ar), 7.84–7.94 (m, 4H, H-Ar), 7.98 (d, 1H, J= 8.9 Hz,
6.38 (brs, 2H, NH2), 7.03 (d, 1H, J= 7.8 Hz, H-Ar), H-Ar). 13C NMR (75 MHz, CDCl3, ppm) ä: 58.93,
7.21 (t, 1H, J=7.8 Hz, H-Ar), 7.35 (d, 1H, J=8.9 Hz, 114.75, 116.82, 119.16, 122.59, 123.55, 125.12,
H-Ar), 7.41–7.54 (m, 3H, H-Ar), 7.70 (d, 1H, J= 8.3 125.73, 127.25, 127.96, 128.15, 128.60, 130.00,
Hz, H-Ar), 7.94 (d, 1H, J= 7.9 Hz, H-Ar), 7.98 (d, 1H, 130.59, 131.48, 147.40, 149.96, 159.79. HR-MS (70
J= 9.0 Hz, H-Ar). HR-MS (70 eV, EI): C20H12N2O35Cl2 eV, EI) C21H13N2OF3 [M]+. found 366.0980; calc.
[M]+. found 366.0319; calc. 366.0327; C20H12N2O35Cl2 366.0967.
[M]+. found 366.0319; calc. 366.0327;

AKANDI et al., Orient. J. Chem., Vol. 30(2), 587-591 (2014)
591
3 - a m i n o - 1 - ( p h e n y l ) - 1 H -
127.67, 128.27, 130.20, 143.06, 145.77, 147.60,
159.89. HR-MS (70 eV, EI): C20H14N2O [M]+. found:
298.11; calc. 298.09
0
benzo[f]chromene-2-carbonitrile, mp: 288-290 C.
1
IR (KBr, cm-1) 3450, 3345, 2180, 1640, 1580. H
NMR (300 MHz, CDCl3, ppm) : 5.30 (s, 1H, H-4),
6.8 (brs, 2H, NH2), 7.23–7.38 (m, 5H, H-Ar), 7.44–
7.48 (m, 5H, H-Ar). 13C NMR (75 MHz, CDCl3, ppm)
 59.08, 111.50, 115.09, 118.33, 119.49, 120.66,
120.86, 123.38, 123.93, 126.44, 126.48, 126.59,
ACKNOWLEDGEMENTS
The authors would like to acknowledge
the support provided by the Research Council of
Islamic Azad University.
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