Three-component reactions of 7-hydroxy coumarin derivatives, acetylenic esters and aromatic aldehydes in the presence of NEt3

Article abstract of DOI:10.5935/0103-5053.20140252

Three-component reactions of 7-hydroxy-4-methyl coumarin or 7-hydroxy-4-(trifluoromethyl) coumarin, dialkyl acetylenedicarboxylates and aromatic aldehydes in the presence of NEt₃ lead to dialkyl (2E)-2-[aryl(hydroxy)methyl]-3-[(4-methyl-2-oxo-2

Full text of DOI:10.5935/0103-5053.20140252

http://dx.doi.org/10.5935/0103-5053.20140252
J. Braz. Chem. Soc., Vol. 26, No. 2, 218-223, 2015.
Printed in Brazil - ©2015 Sociedade Brasileira de Química
0103 - 5053 $6.00+0.00
Communication
Three-Component Reactions of 7-Hydroxy Coumarin Derivatives, Acetylenic Esters
and Aromatic Aldehydes in the Presence of NEt3
Sakineh Asghari,*,a,b Robabeh Baharfar,a Samaneh Ahangar Darabia and
Reza Mohammadiana
aDepartment of Chemistry and bNano and Biotechnology Research Group, University of
Mazandaran, Babolsar, Iran
Three-component reactions of 7-hydroxy-4-methyl coumarin or 7-hydroxy-4-(trifluoromethyl)
coumarin, dialkyl acetylenedicarboxylates and aromatic aldehydes in the presence of NEt3 lead to
dialkyl (2E)-2-[aryl(hydroxy)methyl]-3-[(4-methyl-2-oxo-2H-chromen-7-yl)oxy]but-2-ene dioate
or dialkyl (2E)-2-[aryl(hydroxy)methyl]-3-{(2-oxo-4-(trifluoromethyl)-2H-chromen-7-yl)oxy}
but-2-ene dioate in good yields under mild reaction conditions.
Keywords: 7-hydroxy coumarins, dialkyl acetylenedicarboxylates, aromatic aldehydes,
three-component reaction
Introduction
7-hydroxycoumarins 1 with acetylenic diesters 2 and
arylaldehydes 3 in the presence of NEt3 in tetrahydrofuran
(THF) at ambient temperature to afford the corresponding
three-component products (1:1:1 adduct) as novel
coumarin derivatives 4 and compound 5 as 1:1 adduct in
good yields (Scheme 1).
Coumarins form an exceptional class of oxygen-
containing heterocyclic compounds, which exhibit
significant biological activities, such as inhibitory of
platelet aggregation,1,2 inhibitory of steroid 5α-reductase,3
inhibitory of HIV-1 protease,4 antibacterial and anticancer
activities.5,6 Coumarin derivatives have been applied
for treatment of various cancerous diseases including
malignant melanoma, leukemia, renal cell carcinoma,
prostate and breast cancer.7-12 Moreover, coumarins were
used as intermediates in the synthesis of chromenes,
coumarones and 2-acylresorcinols.13 Owing to their
important applications, various synthetic methodologies for
the synthesis of coumarin derivatives have been developed.
However, further scientific efforts are still on demand to
seek for synthetic methodologies of novel coumarin-based
scaffolds.
Recently, the reactions of phenols including
phenol, 1-naphthol, 2-naphthol, 8-hydroxyquinoline,
1,6-dihydroxynaphthalene and hydroxybenzaldehydes as
OH-acids with dimethyl acetylenedicarboxylate (DMAD)
in the presence of a catalytic amount of triethylamine,15
pyridine16 and triphenylphosphine17 have been reported.
In continuation of our general interest in the synthesis
of heterocyclic compounds via three-component
reactions,17-20 we have investigated the reactions of
Scheme 1. Preparation of O-substituted coumarin derivatives.
Results and Discussion
Initially, the reaction of 7-hydroxy-4-methyl coumarin
and DMAD with 4-nitro benzaldehyde as a model reaction
was examined in the absence of base at room temperature,
in which the starting materials were recovered intact
without the formation of the expected multi-component
reaction (MCR) product 4. When the reaction was carried
*e-mail: s.asghari@umz.ac.ir

Vol. 26, No. 2, 2015
Asghari et al.
219
out in the presence of NEt3, the expected product 4 (1:1:1
adduct) was formed as light yellow powder. In order
to find the appropriate base for the synthesis of 4a, the
model reaction was investigated in THF using different
bases and the results are presented in Table 1. Although
all the bases (K2CO3, 1,8-diazabicyclo[5.4.0]undec-7-ene
(DBU), 1,4-diazabicyclo[2.2.2]octane (DABCO) and NEt3)
promote the reaction, the highest yield of the product was
obtained using NEt3.
However, 4-trifluoromethylbenzaldehyde under similar
condition unexpectedly gave only compound 5.
Table 3. Three-component reactions of 7-hydroxy-4-methyl
coumarin or 7-hydroxy-4-(trifluoromethyl) coumarin with dialkyl
acetylenedicarboxylates and aromatic aldehydes in the presence of NEt3
in THF
Compound
R
R’
X
Yield of 4a / % Yield of 5a / %
4a
Me
Me
Me
Me
Me
Me
CF3
CF3
CF3
CF3
Me
Me
Me
Me
Me
Me
Me
Me
4-NO2
60
53
50
41
55
51
50
30
42
38
–
35
–
4b
t-Bu 4-NO2
Me 2-NO2
t-Bu 2-NO2
Table 1. Effect of different bases in the synthesis of 4a
4c
47
–
4d
Base
Yield of 4a / %
4e
Me
t-Bu
Me
4-CN
4-CN
4-NO2
42
–
K2CO3
DBU
35
50
40
60
4f
4g
–
DABCO
NEt3
4h
t-Bu 4-NO2
–
4i
Me
Me
Me
Me
Me
2-NO2
4-CN
4-CF3
H
–
DBU: 1,8-diazabicyclo[5.4.0]undec-7-ene; DABCO: 1,4-diazabicyclo[2.2.2]
octane.
4j
–
5
92
94
97
98
97
92
94
5
–
The model reaction was further studied using different
amounts of NEt3 under the same reaction conditions
(Table 2). The results in Table 2 clearly show that 100 mol%
of NEt3 give the highest yield of the product 4a.
5
4-CH3
–
5
Me 4-OCH3
–
5
Me
Me
Me
4-F
4-Cl
4-Br
–
5
–
Table 2. Effect of NEt3 mol% in the synthesis of 4a
5
–
aIsolated yields.
NEt3 / mol%
Yield of 4a / %
50
30
40
45
60
60
A plausible mechanism for the synthesis of compounds
4 and 5 is depicted in Scheme 2. It is assumed that
deprotonation of coumarin 1 by NEt3 generates anion
6 that can subsequently perform Michael addition with
dialkyl acetylenedicarboxylate 2 to give intermediate 7.
Intermediate 7 could either protonate by ammonium salt
to produce compound 5 or react with aldehyde 3 to form
intermediate 8, which then protonates by ammonium salt
to afford the coumarin derivatives 4.
The structure of 4a was deduced from infrared (IR),
1H, 13C, 19F nuclear magnetic resonance (NMR) and mass
spectra, as well as elemental analysis. The IR spectrum
of 4a showed a broad band between 3300-3400 cm-1
corresponding to OH stretching absorption and a strong
peak at 1740 cm-1 attributed to C=O vibrations of the ester
groups. The 1H NMR spectrum of 4a exhibited a doublet
at d 2.44 ppm (4JHH 1.2 Hz) for the methyl group, a singlet
at d 3.32 ppm for the OH group, two singlets at d 3.72
and 3.79 ppm for the two methoxy groups, a singlet at
d 6.02 ppm for the aliphatic methine group (CH), a quartet
at d 6.26 ppm (4JHH 1.2 Hz) for the CH group of heterocyclic
moiety, a doublet of doublet at d 6.94 ppm (3JHH 8.8 Hz,
70
100
In order to examine the scope and limitations of this
method, we extended our study to a variety of aromatic
aldehydes with electron-withdrawing and electron-
donating substituents. The results in Table 3 clearly
indicate the significant role of the substituent groups
of the benzaldehyde ring in the reaction pathway for
the synthesis of three-component products 4a-j (1:1:1
adduct). The reactions of 7-hydroxy-4-methyl coumarin
and DMAD with benzaldehyde and electron-donating
substituted benzaldehydes (X = H, CH3, OCH3, F, Cl,
Br) in the presence of NEt3 in THF at room temperature
did not afford the corresponding product 4 and only
compound 5 (1:1 adduct) was collected as sole product.
Electron-withdrawing substituted benzaldehydes (X = NO2,
CN) reacted with 7-hydroxy-4-methyl or trifluoromethyl
coumarins and dialkyl acetylenedicarboxylates under
similar reaction conditions to give the corresponding
three-component products 4a-j in good yields (38-60%).

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Three-Component Reactions of 7-Hydroxy Coumarin Derivatives, Acetylenic Esters and Aromatic Aldehydes
J. Braz. Chem. Soc.
which migrated to lower field for the Z isomer due to the
anisotropic effect of the adjacent ester group.
1
The H NMR spectrum of the Z-isomer exhibited
a doublet at d 2.42 ppm (4JHH 1.2 Hz) for the methyl
group, two sharp singlets at d 3.74 and 3.81 ppm for the
two methoxy groups and a singlet at d 6.77 ppm for the
olefinic proton, and the spectrum of the E-isomer displayed
a doublet at d 2.46 ppm (4JHH 1.2 Hz) for the methyl
group, two singlets at d 3.73 and 3.92 ppm for the two
methoxy groups and a singlet at d 5.43 ppm for the olefinic
proton. The 13C NMR spectrum of 5 displayed 32 distinct
resonances, in agreement with the presence of two E and Z
geometric isomers. The structure of 5 was further confirmed
by the mass spectrum, which displayed a molecular ion
peak at m/z 318.
Experimental
Materials and methods
Scheme 2. Proposed mechanism of preparation of O-substituted coumarin
derivatives.
Dialkyl acetylenedicarboxylates, aromatic aldehydes
and triethylamine were purchased from Fluka (Buchs,
Switzerland) and used without further purification.
7-Hydroxy coumarin derivatives were prepared by
known methods.21 Melting points were measured on an
Electrothermal 9100 apparatus. IR spectra were recorded
on a FT-IR Bruker vector 22 spectrometer; NMR spectra
were recorded on a Bruker DRX-400AVANCE instrument
4JHH 2.4 Hz), a doublet at d 6.97 ppm (4JHH 2.4 Hz) and a
doublet at d 7.57 ppm (3JHH 8.8 Hz) for the three CH groups
of the benzene ring of coumarin and two doublets at d 7.63
and 8.20 ppm (3JHH 8.4 Hz) for the four CH groups of the
para-substituted benzene ring. The 13C NMR spectrum
of 4a exhibited twenty one signals in agreement with the
proposed structure. The mass spectrum of this compound
displayed a molecular ion peak at m/z 469 (M+, 7) and other
fragments at 437, 378, 287, 176 and 150 in accordance with
the structure of 4a.
1
(400.1 MHz for H, 100.6 MHz for 13C, 376.5 MHz for
19F NMR) with CDCl3 as solvent. Chemical shifts are
given in parts per million (d) relative to tetramethylsilane
(TMS), and coupling constants (J) are reported in hertz
(Hz). Mass spectra were recorded on a Finnigan-Matt 8430
mass spectrometer operating at an ionization potential of
70 eV. Elemental analyses were performed using a Heracus
CHN-O Rapid analyzer.
1
Similarly, the H and 13C NMR spectra of 4b-
4j displayed the expected characteristic resonances related
to their structure.
The structure of the compound 5 is E and Z configuration
isomers, as shown in Scheme 3.
General procedure for the preparation of compounds 4a-j
To a magnetically-stirred solution of 7-hydroxy
coumarin derivatives (2 mmol), aromatic aldehydes
(2 mmol) and NEt3 (2 mmol) in THF (8 mL) a mixture of
dialkyl acetylenedicarboxylate (2 mmol) in THF (2 mL)
was added in 15 min. The reaction mixture was then allowed
to stand at room temperature for 0.5-10 h.After completion
of the reaction as indicated by thin-layer chromatography
(TLC) (n-hexane/EtOAc, 1:1), the solvent was removed
under reduced pressure. The residue was purified by column
chromatography on silica gel (Merck, 230-400 mesh) using
a mixture of n-hexane/EtOAc (1:1) as eluent to afford the
pure product as a light yellow powder.
Scheme 3. Geometric isomers of 5.
Although the carbon-carbon double bond in 5 is
conjugated to the adjacent oxygen atom, the rotation
about the C=C bond for the E and Z isomers is slow on
the NMR time scale at room temperature, as confirmed
1
by H and 13C NMR spectra of 5. The assignment of the
Z-configuration to the major geometric isomer of 5 is
based on the 1H NMR chemical shift of the olefinic proton,

Vol. 26, No. 2, 2015
Asghari et al.
221
Analytical data for dimethyl (2E)-2-[hydroxy(4-nitrophenyl)
methyl]-3-[(4-methyl-2-oxo-2H-chromen-7-yl)oxy]but-2-
enedioate (4a)
1H, J 8.0, 0.8 Hz, Ar–H); 13C NMR (100.6 MHz, CDCl3)
d 18.7, 52.9, 53.1, 66.1, 104.3, 113.0, 113.4, 115.0, 124.6,
126.0, 129.1, 129.3, 133.6, 133.8, 135.3, 142.0, 147.7,
152.2, 154.5, 158.1, 160.7, 161.4, 165.7; MS (EI, 70 eV)
(%) 469 (M+, 7), 392 (19), 364 (16), 348 (32), 333 (18),
316 (13), 277 (23), 259 (30), 230 (12), 202 (16), 176 (81),
148 (100), 120 (33), 59 (49); anal. calcd. for C23H19NO10
(469.41): C, 58.85; H, 4.08; N, 2.98%; found: C, 58.91;
H, 4.11; N, 2.94%.
o
Light yellow powder; m.p. 144-146 C; IR (KBr)
ν
max/cm-1 3388, 3074, 2955, 2853, 1740, 1655, 1568, 1347,
1260, 1090; 1H NMR (400.1 MHz, CDCl3) d 2.44 (d, 3H,
J 1.2 Hz, CH3), 3.32 (s, 1H, OH), 3.72 and 3.79 (2s, 6H,
2OCH3), 6.02 (s, 1H, CH benzylic), 6.26 (q, 1H, J 1.2 Hz,
CH heterocylic), 6.94 (dd, 1H, J 8.8, 2.4 Hz, Ar–H), 6.97
(d, 1H, J 2.4 Hz, Ar–H), 7.57 (d, 1H, J 8.8 Hz, Ar–H), 7.63
(d, 2H, J 8.4 Hz, 2Ar–H), 8.20 (d, 2H, J 8.4 Hz, 2Ar–H);
13C NMR (100.6 MHz, CDCl3) d 18.7, 53.0, 53.2, 68.8,
105.0, 113.2, 113.9, 116.6, 123.8, 126.2, 126.9, 130.8,
144.1, 147.5, 147.6, 152.0, 154.7, 157.7, 160.4, 161.4,
165.7; MS (EI, 70 eV) (%) 469 (M+, 7), 437 (7), 378 (15),
319 (11), 287 (38), 262 (15), 234 (16), 176 (43), 150 (100),
104 (23), 76 (15); anal. calcd. for C23H19NO10 (469.41):
C, 58.85; H, 4.08; N, 2.98%; found: C, 58.79; H, 4.13;
N, 2.95%.
Analytical data for di-tert-butyl (2E)-2-[hydroxy(2-nitrophenyl)
methyl]-3-[(4-methyl-2-oxo-2H-chromen-7-yl)oxy]but-2-
enedioate (4d)
o
Light yellow powder; m.p. 149-151 C; IR (KBr)
ν
max/cm-1 3428, 2925, 2855, 1730, 1611, 1528, 1346, 1265,
1089; 1H NMR (400.1 MHz, CDCl3) d 1.24 and 1.33 (2s,
18H, 2CMe3), 2.43 (d, 3H, J 1.2 Hz, CH3), 3.43 (s, 1H,
OH), 6.23 (q, 1H, J 1.2 Hz, CH heterocylic), 6.49 (s, 1H,
CH benzylic), 6.91 (d, 1H, J 2.4 Hz, Ar–H), 6.95 (dd, 1H,
J 8.2, 2.4 Hz, Ar–H), 7.46 (td, 1H, J 7.4, 1.2 Hz, Ar–H),
7.53 (d, 1H, J 8.8 Hz, Ar–H), 7.68 (td, 1H, J 8.2, 1.2 Hz,
Ar–H), 7.98 (dd, 1H, J 8.4, 1.2 Hz, Ar–H), 8.03 (d, 1H,
J 8.1 Hz, Ar–H); 13C NMR (100.6 MHz, CDCl3) d 18.8,
27.5, 27.6, 66.5, 83.5, 83.7, 105.1, 113.4, 113.5, 115.9,
124.6, 125.6, 128.8, 129.2, 131.7, 133.5, 135.8, 143.5,
147.8, 152.1, 154.6, 158.8, 160.0, 160.8, 164.8; MS (EI,
70 eV) (%) 553 (M+, 1), 423 (2), 316 (15), 201 (26), 176
(100), 148 (100), 119 (15), 91 (25), 57 (21); anal. calcd. for
C29H31NO10 (553.57): C, 62.92; H, 5.64; N, 2.53%; found:
C, 62.88; H, 5.69; N, 2.47%.
Analytical data for di-tert-butyl (2E)-2-[hydroxy(4-nitrophenyl)
methyl]-3-[(4-methyl-2-oxo-2H-chromen-7-yl)oxy]but-2-
enedioate (4b)
o
Light yellow powder; m.p. 147-149 C; IR (KBr)
ν
max/cm-1 3425, 2927, 2856, 1728, 1611, 1568, 1346, 1262,
1093; 1H NMR (400.1 MHz, CDCl3) d 1.26 and 1.36 (2s,
18H, 2CMe3), 2.45 (d, 3H, J 1.2 Hz, CH3), 3.88 (s, 1H,
OH), 5.98 (s, 1H, CH benzylic), 6.26 (q, 1H, J 1.2 Hz, CH
heterocylic), 6.96 (dd, 1H, J 8.6, 2.4 Hz, Ar–H), 7.02 (d,
1H, J 2.4 Hz, Ar–H), 7.57 (d, 1H, J 8.4 Hz, Ar–H), 7.64
(d, 2H, J 8.8 Hz, 2Ar–H), 8.22 (d, 2H, J 8.8 Hz, 2Ar–H);
13C NMR (100.6 MHz, CDCl3) d 18.8, 27.6, 27.7, 68.7,
84.1, 84.2, 105.5, 113.4, 113.9, 116.4, 123.5, 125.9, 126.8,
129.5, 145.5, 147.4, 148.2, 152.0, 154.7, 158.2, 159.9,
160.5, 164.8; MS (EI, 70 eV) (%) 553 (M+, 1), 407 (3), 176
(94), 148 (100), 91 (22), 57 (28); anal. calcd. for C29H31NO10
(553.57): C, 62.92; H, 5.64; N, 2.53%; found: C, 62.85;
H, 5.61; N, 2.58%.
Analytical data for dimethyl (2E)-2-[(4-cyanophenyl)
(hydroxy)methyl]-3-[(4-methyl-2-oxo-2H-chromen-7-yl)oxy]
but-2-enedioate (4e)
o
Light yellow powder; m.p. 138-140 C; IR (KBr)
ν
max/cm-1 3426, 3050, 2925, 2855, 2229, 1735, 1263, 1091;
1H NMR (400.1 MHz, CDCl3) d 2.42 (d, 1H, J 0.8 Hz,
OH), 2.44 (d, 3H, J 1.2 Hz, CH3), 3.72 and 3.79 (2s, 6H,
2OCH3), 5.96 (s, 1H, CH benzylic), 6.26 (q, 1H, J 1.2 Hz,
CH heterocylic), 6.91 (dd, 1H, J 8.8, 2.4 Hz, Ar–H), 6.95
(d, 1H, J 2.4 Hz, Ar–H), 7.56 (d, 1H, J 7.2 Hz, Ar–H), 7.57
(d, 2H, J 8.4 Hz, 2Ar–H), 7.64 (d, 2H, J 8.4 Hz, 2Ar–H);
13C NMR (100.6 MHz, CDCl3) d 18.7, 52.0, 53.2, 68.9,
105.0, 111.9, 113.1, 113.9, 116.6, 118.6, 126.2, 126.7,
130.9, 132.4, 144.1, 145.6, 152.0, 154.7, 157.7, 160.4,
161.5, 165.0. MS (EI, 70 eV) (%) 449 (M+, 19), 417 (12),
358 (42), 319 (23), 287 (100), 259 (15), 242 (11), 214 (13),
187 (52), 148 (45), 130 (88), 102 (29), 59 (8); anal. calcd.
for C24H19NO8 (449.42): C, 64.14; H, 4.26; N, 3.12%;
found: C, 64.07; H, 4.31; N, 3.08%.
Analytical data for dimethyl (2E)-2-[hydroxy(2-nitrophenyl)
methyl]-3-[(4-methyl-2-oxo-2H-chromen-7-yl)oxy]but-2-
enedioate (4c)
o
Light yellow powder; m.p. 104-106 C; IR (KBr)
ν
max/cm-1 3429, 3084, 2956, 2855, 1734, 1610, 1527, 1349,
1262, 1085; 1H NMR (400.1 MHz, CDCl3) d 2.41 (d, 3H,
J 0.8 Hz, CH3), 3.37 (s, 1H, OH), 3.68 and 3.77 (2s, 6H,
2OCH3), 6.20 (q, 1H, J 1.2 Hz, CH heterocylic), 6.48
(1H, s, CH benzylic), 6.76 (d, 1H, J 2.4 Hz, Ar–H), 6.87
(dd, 1H, J 8.8, 2.4 Hz, Ar–H), 7.43 (td, 1H, J 7.4, 1.2 Hz,
Ar–H), 7.51 (d, 1H, J 8.8 Hz, Ar–H), 7.67 (td, 1H, J 8.0,
1.2 Hz,Ar–H), 7.91 (dd, 1H, J 8.0, 1.2 Hz,Ar–H), 8.00 (dd,

222
Three-Component Reactions of 7-Hydroxy Coumarin Derivatives, Acetylenic Esters and Aromatic Aldehydes
J. Braz. Chem. Soc.
Analytical data for di-tert-butyl (2E)-2-[(4-cyanophenyl)
(hydroxy)methyl]-3-[(4-methyl-2-oxo-2H-chromen-7-yl)oxy]
but-2-enedioate (4f)
8.24 (d, 2H, J 8.2 Hz, 2Ar–H); 13C NMR (100.6 MHz,
CDCl3) d 27.6, 27.7, 68.8, 84.3, 84.4, 105.7, 109.7, 114.3,
114.5 (q, J 5.6 Hz, CH), 120.3 (q, J 217.5 Hz, CF3), 123.6,
126.8, 126.9 (q, J 2.9 Hz, C), 130.6, 141.2 (q, J 31.2 Hz, C),
144.6, 147.5, 147.8, 155.7, 158.5, 159.2, 159.6, 164.6; MS
(EI, 70 eV) (%) 607 (M+, 2), 495 (29), 432 (8), 403 (4), 345
(13), 316 (9), 230 (96), 202 (28), 175 (8), 151 (39), 105 (5),
57 (100); anal. calcd. for C29H28F3NO10 (607.54): C, 57.33;
H, 4.65; N, 2.31%; found: C, 57.29; H, 4.72; N, 2.26%.
o
Light yellow powder; m.p. 129-131 C; IR (KBr)
ν
max/cm-1 3431, 2925, 2855, 2230, 1728, 1610, 1261,
1
1095; H NMR (400.1 MHz, CDCl3) d 1.28 and 1.34
(2s, 18H, 2CMe3), 2.45 (d, 3H, J 0.8 Hz, CH3), 3.78 (d,
1H, J 8.8 Hz, OH), 5.93 (d, 1H, J 7.6 Hz, CH benzylic),
6.26 (q, 1H, J 1.2 Hz, CH heterocylic), 6.94 (dd, 1H,
J 8.8, 2.8 Hz, Ar–H), 7.02 (d, 1H, J 2.4 Hz, Ar–H), 7.56
(d, 1H, J 8.4 Hz, Ar–H), 7.58 (d, 2H, J 8.4 Hz, 2Ar–H),
7.66 (d, 2H, J 8.4 Hz, 2Ar–H); 13C NMR (100.6 MHz,
CDCl3) d 18.8, 27.7, 29.7, 68.8, 84.0, 84.1, 105.5, 111.5,
113.3, 113.9, 116.4, 118.7, 125.9, 126.7, 129.7, 132.1,
145.4, 146.2, 151.9, 154.7, 158.2, 159.9, 160.5, 164.9; MS
(EI, 70 eV) (%) 533 (M+, 2), 459 (3), 433 (13), 403 (4),
358 (4), 316 (7), 288 (4), 227 (17), 176 (100), 148 (80),
130 (30), 102 (18), 57 (16); anal. calcd. for C30H31NO8
(533.58): C, 67.53; H, 5.86; N, 2.63%; found: C, 67.58;
H, 5.90; N, 2.59%.
Analytical data for dimethyl (2E)-2-[hydroxy(2-nitrophenyl)
methyl]-3-{(2-oxo-4-(trifluoromethyl)-2H-chromen-7-yl)oxy}
but-2-enedioate (4i)
Lightyellowpowder;m.p.142-144˚C;IR(KBr)νmax/cm-1
3448, 3098, 2975, 2855, 1737, 1612, 1529, 1349, 1265,
1083; 1H NMR (400.1 MHz, CDCl3) d 3.1 (s, 1H, OH), 3.71
and 3.78 (2s, 6H, 2OCH3), 6.46 (s, 1H, CH benzylic), 6.72
(s, 1H, CH heterocylic), 6.85 (d, 1H, J 2.8 Hz, Ar–H), 6.92
(dd, 1H, J 8.8, 2.4 Hz, Ar–H), 7.46 (td, 1H, J 7.8, 1.2 Hz,
Ar–H), 7.64-7.70 (m, 2H, 2Ar–H), 7.94 (dd, 1H, J 8.4,
1.2 Hz, Ar–H), 8.00 (d, 1H, J 6.8 Hz, Ar–H); 13C NMR
(100.6 MHz, CDCl3) d 52.9, 53.2, 66.2, 104.7, 109.5, 113.8,
114.1 (q, J 5.3 Hz, CH), 119.1, 121.4 (q, J 280.7 Hz, CF3),
124.6, 126.8, 129.2, 129.3, 133.7, 134.9, 135.1, 141.2 (q,
J 34.4 Hz, C), 147.7, 155.6, 158.7, 159.0, 161.1, 165.5;
MS (EI, 70 eV) (%) 523 (M+, 1), 492 (3), 446 (24), 418
(23), 402 (60), 371 (11), 331 (21), 241 (100), 202 (41),
173 (23), 157 (52), 59 (28); anal. calcd. for C23H16F3NO10
(523.38): C, 52.78; H, 3.08; N, 2.68%; found: C, 52.82;
H, 3.05; N, 2.70%.
Analytical data for dimethyl (2E)-2-[hydroxy(4-nitrophenyl)
methyl]-3-{(2-oxo-4-(trifluoromethyl)-2H-chromen-7-yl)oxy}
but-2-enedioate (4g)
Lightyellowpowder;m.p.168-170oC;IR(KBr)νmax/cm-1
3513, 3089, 2955, 2852, 1739, 1567, 1346, 1263, 1088;
1H NMR (400.1 MHz, CDCl3) d 3.58 (m, 1H, OH), 3.75
and 3.80 (2s 6H, 2OCH3), 5.98 (s, 1H, CH benzylic),
6.76 (s, 1H, CH heterocylic), 7.00-7.03 (m, 2H, 2Ar–H),
7.62 (d, 2H, J 8.4 Hz, 2Ar–H), 7.72 (dd, 1H, J 8.0,
2.0 Hz, Ar–H), 8.21 (d, 2H, J 8.8 Hz, 2Ar–H); 13C NMR
(100.6 MHz, CDCl3) d 53.1, 53.4, 68.9, 105.2, 110.0,
113.9, 114.5 (q, J 5.5 Hz, CH), 121.3 (q, J 275.6 Hz, CF3),
123.8, 126.9, 127.2, 132.3, 141.1 (q, J 33.4 Hz, C), 142.9,
147.0, 147.7, 155.7, 158.5, 158.7, 161.1, 165.5; 19F NMR
(376.5 MHz, CDCl3) d –64.77; MS (EI, 70 eV) (%) 523
(M+, 3), 432 (22), 341 (89), 241 (39), 202 (74), 173 (12),
150 (100), 104 (21), 59 (16); anal. calcd. for C23H16F3NO10
(523.38): C, 52.78; H, 3.08; N, 2.68%; found: C, 52.84;
H, 3.04; N, 2.61%.
Analytical data for dimethyl (2E)-2-[(4-cyanophenyl)
(hydroxy)methyl]-3-{(2-oxo-4-(trifluoromethyl)-2H-chromen-
7-yl)oxy}but-2-enedioate (4j)
Lightyellowpowder;m.p.142-144oC;IR(KBr)νmax/cm-1
3398, 3081, 2960, 2853, 2238, 1728, 1613, 1262, 1062;
1H NMR (400.1 MHz, CDCl3) d 3.1 (s, 1H, OH), 3.74 and
3.80 (2s, 6H, 2OCH3), 5.92 (s, 1H, CH benzylic), 6.75 (s,
1H, CH heterocylic), 6.99-7.01 (m, 2H, 2Ar–H), 7.56 (d,
2H, J 8.4 Hz, 2Ar–H), 7.65 (d, 2H, J 8.0 Hz, 2Ar–H), 7.71
(d, H, J 8.0 Hz, Ar–H); 13C NMR (100.6 MHz, CDCl3)
d 53.1, 53.3, 69.0, 105.1, 112.1, 113.9, 114.5 (q, J 5.7 Hz,
CH), 118.5, 121.3 (q, J 275.5 Hz, CF3), 126.7, 127.1 (q,
J 2.1 Hz, C), 129.1 (q, J 5.1 Hz, C), 132.4, 133.0, 141.1
(q, J 32.9 Hz, C), 142.5, 145.2, 155.7, 158.5, 158.8, 161.4,
165.5; 19F NMR (376.5 MHz, CDCl3) d –64.76; MS (EI,
70 eV) (%) 503 (M+, 3), 471 (4), 439 (5), 412 (29), 373
(37), 341 (100), 313 (11), 241 (41), 202 (20), 182 (18), 157
(15), 130 (69), 102 (15), 59 (6); anal. calcd. for C24H16F3NO8
(503.39): C, 57.27; H, 3.20; N, 2.78%; found: C, 57.31;
H, 3.23; N, 2.69%.
Analytical data for di-tert-butyl (2E)-2-[hydroxy(4-nitrophenyl)
methyl]-3-{(2-oxo-4-(trifluoromethyl)-2H-chromen-7-yl)oxy}
but-2-enedioate (4h)
Lightyellowpowder;m.p.143-145oC;IR(KBr)νmax/cm-1
3488, 2980, 2856, 1748, 1728, 1567, 1346, 1266, 1085;
1H NMR (400.1 MHz, CDCl3) d 1.31 and 1.36 (2s, 18H,
2CMe3), 3.78 (d, 1H, J 9.2 Hz, OH), 5.98 (d, 1H, J 8.4 Hz,
CH benzylic), 6.76 (s, 1H, CH heterocylic), 7.04 (d, 1H,
J 2.4 Hz,Ar–H), 7.07 (dd, 1H, J 6.6, 2.4 Hz,Ar–H), 7.63 (d,
2H, J 8.4 Hz, 2Ar–H), 7.72 (dd, 1H, J 7.2, 1.6 Hz, Ar–H),

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Asghari et al.
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Analytical data for dimethyl 2-[(4-methyl-2-oxo-2H-chromen-
7-yl)oxy]but-2-enedioate (5)
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White powder; m.p. 110-112 C; IR (KBr) νmax/cm-1
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We are thankful to the Research Council of Mazandaran
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Submitted: September 2, 2014
Published online: October 31, 2014