Microwave-assisted synthesis of 8-aryl-10-chloro-4-methyl-2-oxo-2,8-dihydropyrano[2,3-f]chromene-9-carbaldehydes and their antimicrobial activity

Article abstract of DOI:10.1134/S1070363214110322

A series of new coumarin-chromene hybrids have been synthesized by conventional and microwave irradiation methods from 8-aryl-4-methyl-8,9-dihydropyrano[2,3-f]chromene-2,10-diones using the Vilsmeier-Haack reagent. All the synthesized compounds were chara

Full text of DOI:10.1134/S1070363214110322

ISSN 1070-3632, Russian Journal of General Chemistry, 2014, Vol. 84, No. 11, pp. 2234–2239. © Pleiades Publishing, Ltd., 2014.
Microwave-Assisted Synthesis of 8-Aryl-10-chloro-4-methyl-
2-oxo-2,8-dihydropyrano[2,3-f]chromene-9-carbaldehydes
and Their Antimicrobial Activity1
D. Ashoka, B. Vijaya Lakshmia, Arram Ganesha, S. Ravia, S. Adamb, and S. D. S. Murthyb
a Department of Chemistry, Osmania University, Hyderabad, India
b Department of Biochemistry, Sri Venkateswara University, Tirupati, India,
e-mail: ashokdou@gmail.com
Received May 10, 2014
Abstract—A series of new coumarin–chromene hybrids have been synthesized by conventional and
microwave irradiation methods from 8-aryl-4-methyl-8,9-dihydropyrano[2,3-f]chromene-2,10-diones using the
Vilsmeier–Haack reagent. All the synthesized compounds were characterized by IR, 1H NMR, 13C NMR, MS,
and elemental analyses and were screened for antibacterial and antifungal activity. Among the compounds
tested, methoxy-substituted pyranochromenones revealed the best antimicrobial profile.
Keywords: Coumarin, chromene, chromenecarbaldehyde, pyranochromene, Vilsmeier–Haack reaction
DOI: 10.1134/S1070363214110322
The coumarin and chromene moieties are important
six-membered oxygen heterocyclic motifs embedded
in several natural products and drugs. These systems
are widely distributed in nature, and their derivatives
have been shown to exhibit significant pharma-
cological activities [1]. Chromenes and fused chro-
menes are biologically important compounds due to
their antibacterial [2], antifungal [3], antitumor [4], and
antiviral [5] activity. Coumarin derivatives have been
reported to exhibit antiinflammatory [6, 7],
antimicrobial [8], antioxidant [9], anticancer [10], and
chemoprophylactic [11] activities. Hybrid compounds
containing both coumarin and chromene moieties,
called pyranochromenones, may exhibit good biolo-
gical activity due to combined effect. Patil et al. [12]
reported that such pyranochromenone derivatives as
Soulattrolide, Inophyllum G-1, Cordatolide A, and
Oblongulide are potential anti-HIV agents.
OH
O
O
O
O
O
O
O
O
HO
O
O
OCH3
O
O
OH
O
O
O
O
Soulattrolide
Inophyllum G-1
Cordatolide A
Oblongulide
Microwave irradiation is known to provide
enhanced reaction rate and improved product yield in
chemical syntheses and is quite successful in the
formation of a variety of carbon–heteroatom bonds. In
recent years, microwaves have been extensively used
for carrying out chemical reactions and have become a
useful non-conventional energy source for performing
organic syntheses [13, 14].
We reported previously on some 4-chlorochrome-
none derivatives which are potential biologically active
compounds [15]. Encouraged by the pharmacological
activities of pyranochromenones, we wish to report the
synthesis of some new analogs by simple and
convenient microwave irradiation method. Pyranochro-
menone derivatives IIIa–IIIj were synthesized from 8-
acetyl-7-hydroxy-4-methyl-2H-chromen-2-one (I) and
were screened for antimicrobial activity.
The synthetic route to compounds IIIa–IIIj is
shown in Scheme 1. Compounds IIa–IIj were
1 The text was submitted by the authors in English.
2234

MICROWAVE-ASSISTED SYNTHESIS
2235
Scheme 1. Synthetic route for the preparation of pyranochromene derivatives IIIa–IIIj
7
O
6
8
O
Ar
Ar
OH
5
9
4
Ar-CHO
DMF, POCl3
MWI
CHO
O
O
O
10Cl
piperidine
MWI
O
O
3
1
O
2O
O
IIIa−IIIj
IIa−IIj
For Ar, see Table 1.
I
synthesized as reported in [16]. The reaction of 8-
acetyl-7-hydroxy-4-methylcoumarin with aromatic or
heteroaromatic aldehydes in the presence of piperidine
at room temperature gave the corresponding flava-
nones, 8-aryl-4-methyl-8,9-dihydropyrano[2,3-f]chromene-
2,10-diones IIa–IIj which were brought into
Vilsmeier–Haack reaction with DMF/POCl3 [17] at
room temperature to obtain 8-aryl-10-chloro-4-methyl-
2-oxo-2,8-dihydropyrano[2,3-f]chromene-9-carbaldehydes
IIIa–IIIj. On the basis of spectral data, compound IIIa
was identified as 10-chloro-4-methyl-2-oxo-8-phenyl-
2,8-dihydropyrano[2,3-f]chromene-9-carbaldehyde.
The peak at 1078 cm–1 in the IR spectrum of IIIa
confirmed the presence of C–O–C group, and the peak
at 735 cm–1 confirmed the presence of chlorine. The
The synthesis of 10-chloro-4-methyl-2-oxo-8-phenyl-
2,8-dihydropyrano[2,3-f]chromene-9-carbaldehyde (IIIa)
in multiSYNTH microwave system was optimized by
varying irradiation power and reaction time. It was
found that irradiation at a power of 100 W over a
period of 5–6 min (Table 1) ensured the best yield of
IIIa. The microwave-assisted reaction required a
smaller amount of DMF than conventional method.
Also, we compared the yields of the Vilsmeier–Haack
reaction under both conventional heating and MW
irradiation. In all cases, higher yields were obtained
under MW irradiation (Table 1).
Newly synthesized compounds IIIa–IIIj (Table 2)
were screened for their antibacterial activity against
different types of bacterial strains (Figs. 1, 2), including
Gram negative bacterial strains of Escherichia coli and
Pseudomonas aeruginosa and Gram positive strains of
Staphylococcus aureus and Bacillus subtilis, at a
concentration of 100 µg/mL.
1
signals at δ 6.44 ppm (8-H) in the H NMR spectrum
and at δC 73.2 (C8) in the 13C NMR spectrum of IIIa
confirmed the formation of pyranochromenone
skeleton. The base peak in the mass spectrum of IIIa
appeared at m/z 353 due to [M + H]+ ion.
Table 1. Synthesis of pyranochromene derivatives IIIa–IIIj
Conventional heating
Microwave irradiation
time, min yield, %
80
Compound
Ar
no.
time, h
yield, %
68
IIIa
IIIb
IIIc
IIId
IIIe
IIIf
IIIg
IIIh
IIIi
Ph
6
6
7
6
7
6
6
8
6
8
5
4-MeOC6H4
3,4-(MeO)2C6H4
3,4,5-(MeO)3C6H4
2-ClC6H4
65
62
65
60
65
68
65
64
62
6
6
6
5
6
5
6
6
6
82
80
85
82
85
82
83
86
80
4-MeC6H4
4-BrC6H4
4-i-PrC6H4
4-FC6H4
IIIj
1-Naphthyl
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 11 2014

2236
ASHOK et al.
35
30
35
1
4
3
30
25
25
20
2
1
20
15
2
15
10
5
10
5
3
0
0
Compound no.
Compound no.
Fig. 1. Antibacterial activity against gram positive and
gram negative bacterial strains: (1) S. aureus, (2) B. subtilis,
(3) P. Aeruginosa, and (4) E. coli.
Fig. 2. Antifungal activity against pathogenic fungal
strains: (1) Aspergillus nigerzeae, (2) Penicillium italicum,
and (3) Fusarium oxysporum.
Compounds IIIc and IIId showed high activity
against Staphylococcus aureus, and compounds IIIb–
IIId, IIIg, IIIh, and IIIj showed better activity against
Bacillus subtilis compared to standard drug Amoxicilin
at a concentration of 100 µg/mL.
compounds IIIc and IIId exhibit a broad spectrum of
antibacterial activity against all the tested strains.
The antifungal activity of compounds IIIa–IIIj was
tested against three pathogenic fungi (Table 3), namely
Aspergillus nigerzeae, Pencillium italicum, and
Fusarium oxysporum at a concentration of 100 µg/mL
using Mycostatin as reference drug. Compounds IIIc
and IIId were highly active against Aspergillus
nigerzeae, compounds IIIc–IIIg showed high activity
against Pencillium italicum, and compounds IIIb and
Among Gram negative bacterial strains, compounds
IIIc and IIId showed high activity against Escherichia
coli, and the antibacterial activity of IIIa, IIIc–IIIf,
IIIh, and IIIj against Pseudomonas aeruginosa was
comparable to that of Amoxicilin. It is seen that
Table 3. Antifungal activity (inhibition zone, mm) of
compounds IIIa–IIIj at a concentration of 100 μg/mL
Table 2. Antibacterial activity (inhibition zone, mm) of
compounds IIIa–IIIj at a concentration of 100 μg/mL
Gram positive
Gram negative
Compound
no.
Compound
no.
Aspergillus
nigerzeae
Penicillium
italicum
Fusarium
oxysporum
P.
S. aureus B. subtilis
E. coli
aeruginosa
IIIa
20
28
30
33
22
20
22
15
11
20
30
08
10
12
15
07
08
10
10
08
11
12
08
22
25
32
30
25
23
22
20
10
14
30
IIIa
08
09
11
14
09
09
06
08
08
09
12
16
15
20
24
20
21
18
15
14
17
20
22
25
22
28
26
23
23
20
19
14
25
IIIb
IIIc
07
09
11
10
09
07
08
04
08
10
IIIb
IIIc
IIId
IIIe
IIId
IIIe
IIIf
IIIf
IIIg
IIIg
IIIh
IIIi
IIIh
IIIi
IIIj
IIIj
Amoxicilin
Mycostatin
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 11 2014

MICROWAVE-ASSISTED SYNTHESIS
2237
IIId–IIIg showed high activity against Fusarium
oxysporum. Compound IIId showed a broad spectrum
of antifungal activity against all the tested strains.
b. Microwave-assisted reaction. A round-bottom
flask was charged with 2 mL of DMF and cooled to 0–
5°C, 0.006 mol of phosphoryl chloride was added
dropwise under stirring, the mixture was stirred for
15 min at 0 to 5°C, and a solution of 0.001 mol of 8-
aryl-4-methyl-8,9-dihydropyrano[2,3-f]chromene-2,10-
dione IIa–IIj in 2 mL of DMF was added. The mixture
was maintained for 30 min at 0 to 5°C and was then
irradiated in a multiSYNTH microwave furnace at
100 W over a period indicated in Table 1. When the
reaction was complete (TLC, EtOAc–hexane, 1 : 3 by
volume), the mixture was poured into ice water,
neutralized with 10% aqueous NaOH, and extracted
with chloroform. The combined extracts were washed
with water and dried over anhydrous magnesium
sulfate. The solvent was evaporated, and the residue
was purified by silica gel column chromatography to
afford pure product IIIa–IIIj.
In summary, we have synthesized a series of new 8-
aryl-10-chloro-4-methyl-2-oxo-2,8-dihydropyrano-
[2,3-f]chromene-9-carbaldehydes IIIa–IIIj by con-
ventional and microwave irradiation methods. The
reactions under microwave irradiation were completed
in shorter time with better yields than under conven-
tional conditions. Screening of the new compounds for
antimicrobial and antifungal activity revealed broad
spectrum of antibacterial activity of IIIc and IIId and
broad spectrum of antifungal activity of IIId.
EXPERIMENTAL
All used materials were commercial products
purchased mostly from Sigma Aldrich and were used
without further purification. The melting points were
determined in open capillaries and are uncorrected.
The purity of the newly synthesized compounds was
checked by TLC on silica gel 60 F254 (Merck). The
1H NMR and 13C NMR spectra were recorded on a
Bruker Avance II 400 spectrometer using tetra-
methylsilane as internal standard. The IR spectra were
recorded in KBr on a Shimadzu FTIR 8400S spec-
trometer. The mass spectra were obtained on a
Shimadzu GCMS-QP 1000 instrument. Microwave-as-
sisted reactions were carried out in a Milestone multi-
SYNTH microwave system.
10-Chloro-4-methyl-2-oxo-8-phenyl-2,8-dihydro-
pyrano[2,3-f]chromene-9-carbaldehyde (IIIa). Yield
80%, mp 198–200°C. IR spectrum, ν, cm–1: 737 (C–Cl),
1
1078 (C–O–C), 1745 (CH=O). H NMR spectrum, δ,
ppm: 2.31 d (3H, CH3, J = 1.004 Hz), 5.98 d (1H, 3-H,
J = 1.004 Hz), 6.52 s (1H, 8-H), 6.98 d (1H, 6-H, J =
8.78 Hz,), 7.27–7.36 m (5H, Harom), 7.54 d (1H, 5-H,
J = 8.78 Hz), 9.66 s (1H, CHO). 13C NMR spectrum,
δC, ppm: 18.9 (CH3), 73.2 (C8), 112.3, 114.1, 114.9,
126.8, 128.5, 128.6, 129.0, 130.1, 137.4, 147.6, 151.9,
152.2, 157.9, 158.6, 162.0, 164.5 (C=O), 190.1 (CHO).
Mass spectrum: m/z 353 [M + H]+. Found, %: C 68.14;
H 3.76; C20H13ClO4. Calculated, %: C 68.09; H 3.71.
General procedures for the synthesis of 8-aryl-
10-chloro-4-methyl-2-oxo-2,8-dihydropyrano[2,3-f]-
chromene-9-carbaldehydes IIIa–IIIj. a. Conven-
tional method. A round-bottom flask was charged with
5 mL of DMF and cooled to 0–5°C, 0.006 mol of
phosphoryl chloride was added dropwise under
stirring, the mixture was stirred for 15 min at 0 to 5°C,
and a solution of 0.001 mol of 8-aryl-4-methyl-8,9-
dihydropyrano[2,3-f]chromene-2,10-dione IIa–IIj in
3 mL of DMF was added. The mixture was stirred for
30 min at 0 to 5°C and for 6 to 8 h at room temperature
(Table 1). When the reaction was complete (TLC,
EtOAc–hexane, 1 : 3 by volume), the mixture was
poured into ice water, neutralized with 10% aqueous
NaOH, and extracted with chloroform. The combined
extracts were washed with water and dried over
anhydrous magnesium sulfate. The solvent was
evaporated, and the residue was purified by silica gel
column chromatography to afford pure product IIIa–
IIIj.
10-Chloro-8-(4-methoxyphenyl)-4-methyl-2-oxo-
2,8-dihydropyrano[2,3-f]chromene-9-carbaldehyde
(IIIb). Yield 82%, mp 206–208°C. IR spectrum, ν,
1
cm–1: 737 (C–Cl), 1088 (C–O–C), 1725 (CH=O). H
NMR spectrum, δ, ppm: 2.38 d (3H, CH3, J = 1.004 Hz),
3.80 s (3H, OCH3), 6.11 d (1H, 3-H, J = 1.004 Hz),
6.18 s (1H, 8-H), 6.85 d (1H, 6-H, J = 8.78 Hz), 6.89 d
(2H, Harom, J = 8.55 Hz), 7.38 d (2H, Harom, J = 8.55 Hz),
7.46 d (1H, 5-H, J = 8.78 Hz), 9.89 s (1H, CHO). 13C
NMR spectrum, δC, ppm: 19.0 (CH3), 55.3, 78.4 (C8),
109.6, 112.3, 113.3, 114.1 114.9, 124.6, 125.5, 126.4,
129.0, 129.8, 150.2, 152.3, 157.3, 160.0, 160.2 (C=O),
192.8 (CHO). Found, %: C 65.93; H 3.98. C21H15ClO5.
Calculated, %: C 65.89; H 3.95. Mass spectrum: m/z
383 [M + H]+.
10-Chloro-8-(3,4-dimethoxyphenyl)-4-methyl-2-
oxo-2,8-dihydropyrano[2,3-f]chromene-9-carbalde-
hyde (IIIc). Yield 80%, mp 190–192°C. IR spectrum,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 11 2014

2238
ASHOK et al.
ν, cm–1: 739 (C–Cl), 1086 (C–O–C), 1725 (CH=O). 1H
NMR spectrum, δ, ppm: 2.38 d (3H, CH3, J = 1.004 Hz ),
3.87 s and 3.89 (s (3H each, OCH3), 5.78 s (1H, 8-H),
6.19 d (1H, 3-H, J = 1.004 Hz), 6.84 d (1H, 6-H, J =
8.78 Hz), 6.85–7.26 m (3H, Harom), 7.46 d (1H, 5-H,
J = 8.78 Hz), 9.49 s (1H, CHO). 13C NMR spectrum,
δC, ppm: 19.02 (CH3), 55.9, 56.0, 77.9 (C8), 109.6,
110.4, 112.3, 113.2, 114.9, 120.2, 124.6, 125.5, 126.5,
130.1, 149.1, 149.6, 150.2, 152.5, 157.2, 160.0 (C=O),
190.2 (CHO). Found, %: C 64.05; H 4.19. C22H17ClO6.
Calculated, %: C 64.01; H 4.15. Mass spectrum: m/z
413 [M + H]+.
7.92 d (1H, 5-H, J = 8.78 Hz), 9.63 s (1H, CHO). 13C
NMR spectrum, δC, ppm: 19.0 (CH3), 21.2, 77.8 (C8),
112.3, 113.2, 124.6, 125.4, 126.2, 126.4, 127.3, 129.1,
129.5, 129.8, 134.9, 139.0, 152.9, 157.3, 160.0 (C=O),
190.3 (CHO). Found, %: C 68.80; H 4.15. C21H15ClO4.
Calculated, %: C 68.76; H 4.12. Mass spectrum: m/z
367 [M + H]+.
8-(4-Bromophenyl)-10-chloro-4-methyl-2-oxo-
2,8-dihydropyrano[2,3-f]chromene-9-carbaldehyde
(IIIg). Yield 82%, mp 204–206°C. IR spectrum, ν, cm–1:
1
735 (C–Cl), 1076 (C–O–C), 1738 (CH=O). H NMR
spectrum, δ, ppm: 2.38 s (3H, CH3, J = 1.004 Hz), 6.07
d (1H, 3-H, J = 1.004 Hz), 6.23 s (1H, 8-H), 6.86 d
(1H, 6-H, J = 8.78 Hz), 6.95 d (2H, Harom, J = 8.56 Hz),
6.97 d (2H, Harom, J = 8.56 Hz), 7.47 d (1H, 5-H, J =
8.78 Hz), 9.63 s (1H, CHO). 13C NMR spectrum, δC,
ppm: 19.3 (CH3), 73.7 (C8), 112.7, 114.0, 115.2, 120.2,
122.3, 122.9, 124.5, 126.9, 128.6, 129.0, 129.1, 129.6,
134.4, 136.1, 152.4, 158.4, 159.3 (C=O), 188.8 (CHO).
Found, %: C 55.68; H 2.83. C20H12BrClO4. Calculated,
%: C 55.65; H 2.80. Mass spectrum: m/z 431 [M + H]+.
10-Chloro-4-methyl-2-oxo-8-(3,4,5-trimethoxy-
phenyl)-2,8-dihydropyrano[2,3-f]chromene-9-carbal-
dehyde (IIId). Yield: 85%, mp 206–208°C. IR
spectrum, ν, cm–1: 741 (C–Cl), 1088 (C–O–C), 1727
(CH=O). 1H NMR spectrum, δ, ppm: 2.38 d (3H, CH3,
J = 1.004 Hz), 3.80 s (3H, OCH3), 3.84 s (6H, OCH3),
6.22 d (1H, 3-H, J = 1.004 Hz), 6.42 s (1H, 8-H), 7.23
d (1H, 6-H, J = 8.78 Hz), 7.37 s (2H, Harom), 7.52 d
(1H, 5-H, J = 8.78 Hz), 10.42 s (1H, CHO). 13C NMR
spectrum, δC, ppm: 19.3 (CH3), 54.6, 56.2, 76.8 (C8),
110.5, 112.7, 113.2, 114.6, 121.4, 123.6, 126.5, 132.4,
148.9, 149.6, 150.2, 152.5, 160.0, 162.2 (C=O), 190.5
(CHO). Found, %: C 62.42; H 4.36. C23H19ClO7.
Calculated, %: C 62.38; H 4.32. Mass spectrum: m/z
443 [M + H]+.
10-Chloro-8-(4-isopropylphenyl)-4-methyl-2-oxo-
2,8-dihydropyrano[2,3-f]chromene-9-carbaldehyde
(IIIh). Yield 83%, mp 166–168°C. IR spectrum, ν,
1
cm–1: 750 (C–Cl), 1088 (C–O–C), 1725 (CH=O). H
NMR spectrum, δ, ppm: 1.46 s (6H, CH3) 2.38 d (3H,
J = 1.004 Hz), 2.45 m [1H, CH(CH3)2], 6.08 d (1H,
3-H, J = 1.004 Hz), 6.54 s (1H, 8-H), 6.87 d (1H, 6-H,
J = 8.78 Hz), 7.25–7.27 d (2H, Harom, J = 8.64), 7.32 d
(2H, J = 8.64 Hz), 7.54 d (1H, 5-H, J = 8.78 Hz),
10.36 s (1H, CHO). 13C NMR spectrum, δC, ppm: 13.2
[CH(CH3)2], 19.0 (CH3), 25.3 [CH(CH3)2], 76.4 (C8),
112.3, 113.9, 120.3, 121.2, 122.2, 123.8, 124.6, 125.5,
126.4, 129.0, 129.8, 150.2, 152.3, 157.3, 160.2 (C=O),
190.2 (CHO). Found, %: C 69.96; H 4.85. C23H19ClO4.
Calculated, %: C 69.92; H 4.81. Mass spectrum: m/z
395 [M + H]+.
10-Chloro-8-(2-chlorophenyl)-4-methyl-2-oxo-2,8-
dihydropyrano[2,3-f]chromene-9-carbaldehyde (IIIe).
Yield 82%, mp 182–184°C. IR spectrum, ν, cm–1: 751
(C–Cl), 1074 (C–O–C), 1736 (CH=O). 1H NMR
spectrum, δ, ppm: 2.37 d (3H, CH3, J = 1.004 Hz),
6.23 d (1H, 3-H, J = 1.004 Hz), 6.83 s (1H, 8-H), 6.84
d (1H 6-H, J = 8.78 Hz), 7.07–7.44 m (4H, Harom), 7.53
d (1H, 5-H, J = 8.78 Hz), 10.36 s (1H, CHO). 13C
NMR spectrum, δC, ppm: 19.3 (CH3), 73.7 (C8), 112.7,
114.0, 115.2, 120.2, 122.3, 122.9, 124.5, 126.9, 128.6,
129.0, 129.1, 129.6, 134.4, 136.1, 152.4, 158.4, 159.3,
162.3 (C=O), 188.8 (CHO). Found, %: C 62.07; H
3.16. C20H12Cl2O4. Calculated, %: C 62.04; H 3.12.
Mass spectrum: m/z 387 [M + H]+.
10-Chloro-8-(4-fluorophenyl)-4-methyl-2-oxo-2,8-
dihydropyrano[2,3-f]chromene-9-carbaldehyde (IIIi).
Yield 86%, mp 200–202°C. IR spectrum, ν, cm–1: 745
1
(C–Cl), 1078 (C–O–C), 1740 (CH=O). H NMR spe-
10-Chloro-4-methyl-8-(4-methylphenyl)-2-oxo-
2,8-dihydropyrano[2,3-f]chromene-9-carbaldehyde
(IIIf). Yield 85%, mp 200–202°C. IR spectrum, ν, cm–1:
ctrum, δ, ppm: 2.36 d (3H, CH3, J = 1.004 Hz), 5.80 d
(1H, 3-H, J = 1.004 Hz), 6.18 s (1H, 8-H), 6.81 d (1H,
6-H, J = 8.78), 6.89 d (2H, Harom, J = 8.72), 7.31 d (2H,
1
739 (C–Cl), 1084 (C–O–C), 1728 (CH=O). H NMR
Harom, J = 8.72 Hz), 7.43 d (1H, 5-H, J = 8.78 Hz),
spectrum, δ, ppm: 2.34 s (3H, CH3, J = 1.004 Hz), 2.36
s (3H, CH3C6H4), 6.01 d (1H, 3-H, J = 1.004 Hz), 6.22
s (1H, 8-H), 7.18 d (1H, 6-H, J = 8.78 Hz), 7.48 d (2H,
9.59 s (1H, CHO). 13C NMR spectrum, δC, ppm: 19.3
(CH3), 73.7 (C8), 112.7, 114.0, 115.2, 120.2, 122.3,
122.9, 124.5, 126.9, 128.6, 129.0, 129.1, 129.6, 134.4,
136.1, 152.4, 158.4, 159.3, 160.2 (C=O), 190.5 (CHO).
Harom, J = 8.53 Hz), 7.76 d (2H, Harom, J = 8.53 Hz),
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 11 2014

MICROWAVE-ASSISTED SYNTHESIS
2239
3. Ohira, T. and Yatagai, M., J. Jpn. Wood Res. Soc.,
Found, %: C 64.82; H 3.30. C20H12ClFO4. Calculated,
%: C 64.79; H 3.26. Mass spectrum: m/z 371 [M + H]+.
1993, vol. 39, p. 231.
4. Mohr, S.J., Chirigos, M.A., Fuhrman, F.S., and Pryor, J.W.,
10-Chloro-4-methyl-8-(naphthalen-1-yl)-2-oxo-
2,8-dihydropyrano[2,3-f]chromene-9-carbaldehyde
(IIIj). Yield 80%, mp 205–207°C. IR spectrum, ν, cm–1:
Cancer Res., 1975, vol. 35, p.3750.
5. Martinez, A.G. and Marco, L.J., Bioorg. Med. Chem.
Lett., 1997, vol. 24, p.3165.
1
756 (C–Cl), 1076 (C–O–C), 1745 (CH=O). H NMR
6. Jung, K., Park, Y.J., and Ryu, J.S., Synth. Commun.,
spectrum, δ, ppm: 2.31 d (3H, CH3, J = 1.004 Hz),
6.20 d (1H, 3-H, J = 1.004 Hz), 6.68 d (1H, 6-H, J =
8.78 Hz), 7.23 s (1H, 8-H), 7.39–7.78 m (5H, Harom),
7.84 d (1H, 5-H, J = 8.78 Hz), 8.13–8.56 m (2H,
2008, vol. 38, p. 4395.
7. Kaczka, E.A., Wolf, F.J., Ratha, F.P., and Folkers, K.J.,
J. Am. Chem. Soc., 1955, vol. 77, p. 6404.
H
arom), 10.45 s (1H, CHO). 13C NMR spectrum, δC,
8. Mulwad, V.V. and Shirodkhar, J.M., Indian J. Hetero-
cycl. Chem., 2002, vol.11, p. 192.
ppm: 19.1 (CH3), 74.7 (C8), 112.7, 114.0, 115.2, 120.2,
121.2, 121.6, 122.3, 122.9, 123.4, 124.5, 126.9, 128.6,
129.0, 129.1, 129.6, 136.1, 152.4, 158.4, 159.3 (C=O),
188.8 (CHO). Found, %: C 71.61; H 3.79. C24H15ClO4.
Calculated, %: C 71.56; H 3.75. Mass spectrum: m/z
403 [M + H]+.
9. Kusanur, R., Manjunath, G., and Kulkarni, M.V., Indian
J. Heterocycl. Chem., 2004, vol. 13, p. 201.
10. Rajeshwar Rao, V., Srimanth, K., and Vijaya Kumar, P.,
Indian J. Heterocycl. Chem., 2004, vol. 14, p. 141.
11. Nofal, Z.M., El-Zahar, M.I., and Abd El-Karim, S.S.,
Egypt. J. Chem., 2005, vol. 48 p. 587.
ACKNOWLEDGMENTS
12. Patil, A.D., Freyer, A.J., Eggleston, D.S., Haltiwanger, R.C.,
Bean, M.F., Taylor, P.B., Caranfa, M.J., Breen, A.L.,
Bartus, H.R., Johnson, R.K., Hertzberg, R.P., and
Westley, J.W., J. Med. Chem., 1993, vol. 36, p. 4131.
The authors are thankful to the Head, Department
of Chemistry, Osmania University, Hyderabad, for
providing Laboratory facilities and the Director,
CFRD, Osmania University, Hyderabad, for providing
spectral analysis facilities. B. Vijaya Lakshmi, is
thankful to CSIR, New Delhi, India, for financial
support in the form of CSIR-SRF.
13. Gedye, R.N. and Wei, J.B., Can. J. Chem., 1998, vol. 76,
p. 525.
14. Varma, R.S., Green Chem., 1999, vol. 1, p. 43.
15. Ashok, D., Sudershan, K., and Khalilullah, M., Indian J.
Heterocycl. Chem., 2012, vol. 21, p. 301.
16. Chand, K., Amir, N.S., Preethi, Y., Rmesh, K., Tiwari, K.,
Meena, K., Keykavous, P. and Sunil, K.S., Can. J.
Chem., 2013, vol. 91, p. 741.
REFERENCES
17. Venkati, M., Satyanarayana Reddy, S., Swamy, G.Y.S.K.,
Ravikumar, K., and Krupadanam, G.L.D., Arkivoc,
2012, part (vi), p. 355.
1. Cassidy, F., Evans, J.M., Hadley, M.S., Haladij, A.H.,
Leach, P.E., and Stemp, G.. J. Med. Chem., 1992,
vol. 35, p.1623.
2. El-Agrody, A.M., El-Hakim, M.H., AbdEl-Latif, M.S.,
Fakery, A.H., El Sayeed, and Ghareeb, El-K.A., Acta
Pharm., 2000, vol. 50, p. 111.
18. Benson, H.J., Microbiological Applications:
A
Laboratory Manual in General Microbiology, Dubuque,
Iowa: W.C. Brown, 1990, 5th ed.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 11 2014