Choline hydroxide as an efficient catalyst for the diastereoselective synthesis of trans-2,3-dihydrofuro[3,2-c]coumarins in an aqueous medium

Article abstract of DOI:10.3184/174751916X14757574219700

A one-pot, three-component condensation of 2-[2-(4-chlorophenyl)-2-oxoethyl]isoquinolinium bromide with 4-hydroxycoumarin and an aromatic aldehyde in the presence of catalytic amounts of choline hydroxide in refluxing water gave trans-2-(4-chlorobenzoyl)-3-(aryl)-2,3-dihydro-4H-furo[3,2-c]chromen-4-ones in excellent yields and with short reaction times.

Full text of DOI:10.3184/174751916X14757574219700

JOURNAL OF CHEMICAL RESEARCH 2016
VOL. 40 NOVEMBER, 655–658
RESEARCH PAPER 655
Choline hydroxide as an efficient catalyst for the diastereoselective synthesis
of trans-2,3-dihydrofuro[3,2-c]coumarins in an aqueous medium
Maryam Salaria, Mohammad H. Mosslemina* and Alireza Hassanabadib
aDepartment of Chemistry, Yazd Branch, Islamic Azad University, Yazd, Iran
bDepartment of Chemistry, Zahedan Branch, Islamic Azad University, Zahedan, Iran
A one-pot, three-component condensation of 2-[2-(4-chlorophenyl)-2-oxoethyl]isoquinolinium bromide with 4-hydroxycoumarin and an
aromatic aldehyde in the presence of catalytic amounts of choline hydroxide in refluxing water gave trans-2-(4-chlorobenzoyl)-3-(aryl)-
2,3-dihydro-4H-furo[3,2-c]chromen-4-ones in excellent yields and with short reaction times.
Keywords: furocoumarins, choline hydroxide, isoquinoline, green chemistry, diastereoselectivity, aryl aldehydes, 4-chlorophenacyl bromide,
4-hydroxycoumarin
Compounds containing the furocoumarin ring system are known
to possess pharmacological properties such as anticancer,1
antifungal,2 antibacterial,3 vasorelaxant,4 antimicrobial5 and
photobiological6 activities. The literature contains reports of
the synthesis of furocoumarins in the presence of aldehydes
and 4-hydroxycoumarin (2 equiv.) in poly(ethyleneglycol)
(PEG) and a mixture of I2 and K2S2O8,7 from the reactions of
aromatic aldehydes, 4-hydroxycoumarin and α-chloroketones
and a mixture of AcOH and AcONH4,8 from the sequential
multicomponent reactions of 4-hydroxycoumarin, aromatic
aldehydes and in situ generated cyanomethylpyridinium and
phenacylpyridinium/(2-ethoxy-2-oxoethyl)pyridinium ylides in
the presence of the ionic liquid [BMIm]OH,9 from the reaction
of pyridine, aromatic aldehyde, dimedone or 4-hydroxycoumarin
and phenacyl bromide or p-nitrobenzyl bromide with Et3N,10 from
aldehydes, a cyclic 1,3-diketone, 2-bromo-1-phenylethanone
and N-methylimidazolium,11 from the alkoxylation of
4-oxohydrocoumarins, alkenes and Pd(CF3COO)2,12 from the
reaction of 4-hydroxycoumarin derivatives with (E)-3-aryl/
hetero-aryl-2-nitroprop-2-enols and 4-dimethylaminopyridine
(DMAP),13 and from the reactions of aryl aldehydes, a cyclic
1,3-diketone, 2-bromo-1-phenylethanone or 4-nitrobenzyl
bromide and pyridine in the presence of 10 mol% sodium
hydroxide in refluxing aqueous solution.14 Although many
of the reported methods are effective, some of them suffer
from disadvantages such as harsh reaction conditions, use of
hazardous solvents, long reaction times, complex working and
purification procedures, high catalyst loadings and moderate
yields. Therefore, the development of a simple, mild and efficient
method is still needed. In the present work, we used choline
hydroxide as an efficient catalyst to overcome these limitations.
Recently, organic reactions in aqueous media have attracted
a great deal of attention15 as a result of increasing interest in
the concepts of sustainability and green chemistry.16 The
latter synthesis used a procedure first described by Wang et
al.10 and by Khan et al.14 in which a series of furocoumarins
were synthesised via the pyridine-catalysed reaction of
phenacyl bromides with a series of aromatic aldehydes and
4-hydroxycoumarin in the presence of catalytic amounts of
NaOH or Et3N. In this study, we have used the procedures of
Wang et al.10 and of Khan et al.14 to synthesise another class
of furocoumarins via a three-component condensation reaction
of 2-[2-(4-chlorophenyl)-2-oxoethyl]isoquinolinium bromide 2
with 4-hydroxycoumarin 3 and an aromatic aldehyde 4 in the
presence of catalytic amounts of choline hydroxide (Scheme 1).
Results and discussion
Treatment of isoquinoline with 4-chlorophenacyl bromide 1 in
acetonitrile after 20 min yielded the 2-[2-(4-chlorophenyl)-2-
oxoethyl]isoquinolinium bromide 2 in nearly quantitative yields
(Scheme 2).
A one-pot, three-component reaction of 2-[2-(4-chlorophenyl)-
2-oxoethyl]isoquinolinium bromide 2 with 4-hydroxycoumarin 3
and an aromatic aldehyde 4 in the presence of catalytic amounts of
choline hydroxide in refluxing water provided the corresponding
products 5 in excellent yields (Scheme 3).
The structures of compounds 5a–l were deduced from
1
their IR and H and 13C NMR spectra. The mass spectra of
compounds 5a–l were fairly similar and displayed molecular
1
ion peaks. In the H NMR spectra the two protons at the
2,3-positions of the dihydrofuran ring displayed two doublets at
5.52 and 5.10 ppm with a vicinal coupling constant J = 4.4 Hz. It
has been documented that in cis-2,3-dihydrofurans the vicinal
coupling constant of the two methine protons is J = 7–10 Hz,
while in the trans-2,3-dihydrofuran the vicinal coupling
constant is J = 2.8–6 Hz. Thus we concluded that the more
thermodynamically stable trans isomers of the 2,3-dihydrofuran
derivatives were formed.14
OH
Cl
O
OH
OH–
N+
H
O
O
O
Br–
3
N+
O
+
Ar
O
H2O, Reflux, 3 h
2
H
Cl
Ar
H
4
O
O
5
Scheme 1
* Correspondent. E-mail: mhmosslemin@gmail.com

656 JOURNAL OF CHEMICAL RESEARCH 2016
O
O
Br
Br–
CH CN3, r.t., 20 min
N+
+
N
Cl
2
1
Cl
Scheme 2
OH
Cl
O
OH
OH–
N+
O
H
O
Br–
O
3
N+
O
+
Ar
H
O
H2O, Reflux, 3 h
2
Cl
Ar
H
O
O
4
5
*
*
m.p./°C
201–203
185–187
m.p./°C
5
a
Ar
C6H5
5
Ar
% Yield
92
% Yield
90
177–179
g
4-CH3O C6H4
4-FC6H4
h
95
92
226–228
235–237
b
c
2-O N
C6H4
C H
93
94
90
2
i
C H
4-Cl-3-O2N
4-NC C6H4
4-O2N
181–183
233–235
249–251
219–221
6
3
6
4
j
194–196
195–197
189–191
90
90
91
d
e
f
C H
6 4
2-Cl
4-CH
3 C6H4
k
l
4-ClC6H4
2-FC6H4
91
94
C H
4-Br
6
4
*Yields refer to the pure isolated products
Scheme 3
H2O
OH
N+
Br–
O
O
Br–
N+
OH
N+
OH–
+
2
N+
Cl
_
6
O
O
OH
O
Cl
O
OH–
Ar
+
Ar
H
O
O
4
3
7
O
N+
_
O
N+
_
6
_
O
O
N
Cl
O
5
Ar
Ar
O
O
O
Cl
7
8
Scheme 4

JOURNAL OF CHEMICAL RESEARCH 2016 657
(KBr) νmax/cm−1: 2931, 2856, 1727, 1640, 1523, 1411, 747, 575; Anal.
calcd for C24H14ClNO6: C, 64.37; H, 3.15; N, 3.13; found: C, 64.23; H,
3.24; N, 3.25%; MS (m/z, %): 447 (6); 1H NMR (400 MHz, CDCl3): δ
5.08 (1H, d, J = 5.2 Hz, H-3), 6.09 (1H, d, J = 5.2 Hz, H-2), 7.36 (2H, m,
Ar-H), 7.38 (1H, t, J = 8.2 Hz, Ar-H), 7.44 (1H, d, J = 8 Hz, Ar-H), 7.55
(2H, d, J = 7.4 Hz, Ar-H), 7.80 (2H, d, J = 7.4 Hz, Ar-H), 7.95 (2H, d,
J = 8 Hz, Ar-H), 8.18 (2H, d, J = 7.6 Hz, Ar-H) ppm; 13C NMR (100.6
MHz, CDCl3): δ 48.0, 92.0, 104.3, 111.7, 117.2, 123.1, 124.4, 125.3,
128.8, 129.4, 130.6, 131.6, 133.5, 141.4, 146.5, 147.7, 155.4, 159.0, 166.4,
190.4 ppm.
A proposed mechanism for this reaction is shown in Scheme
4. The formation of the product can be explained as follows.
The 2-[2-(4-chlorophenyl)-2-oxoethyl]isoquinolinium bromide
2 undergoes deprotonation in the presence of aqueous choline
hydroxide to give the reactive isoquinolinium ylide 6 at room
temperature. The 4-hydroxycoumarin 3 reacts with aromatic
aldehyde 4 in the presence of choline hydroxide to give the
Knoevenagel product 7. The latter reacts instantly with the
isoquinolinium ylide 6 to form the zwitterionic intermediate 8.
The intermediate 8 undergoes cyclisation with the elimination
of isoquinoline to give the desired product 5.
In summary, here we report a simple and efficient one-pot
synthesis of trans-2,3-dihydrofuro[3,2-c]coumarins via a
three-component reaction between 2-[2-(4-chlorophenyl)-2-
oxoethyl]isoquinolinium bromide with 4-hydroxycoumarin and
an aromatic aldehyde in the presence of catalytic amounts of
choline hydroxide. The advantages of this method are simple,
readily available, starting materials, short reaction times, easy
and clean work-up and excellent yields of products.
trans-2-(4-Chlorobenzoyl)-3-(2-chlorophenyl)-2,3-dihydro-4H-
furo[3,2-c]chromen-4-one (5d): White powder, m.p. 233–235 °C;
IR (KBr) νmax/cm−1: 2924, 2843, 1723, 1644, 1450, 1402, 1026, 754,
575; Anal. calcd for C24H14Cl2O4: C, 65.92; H, 3.23; found: C, 65.77;
H, 3.35%; MS (m/z, %): 436 (7); 1H NMR (400 MHz, CDCl3): δ 5.34
(1H, d, J = 5.2 Hz, H-3), 6.07 (1H, d, J = 5.2 Hz, H-2), 7.16–7.30 (3H,
m, Ar-H), 7.34 (1H, d, J = 7.4 Hz, Ar-H), 7.41 (1H, d, J = 7.4 Hz, Ar-
H), 7.49 (1H, t, J = 8.2 Hz, Ar-H), 7.56 (1H, d, J = 7.2 Hz, Ar-H), 7.65
(1H, d, J = 8.2 Hz, Ar-H), 7.80 (2H, d, J = 8.0 Hz, Ar-H), 7.90 (2H, d,
J = 8.0 Hz, Ar-H) ppm; 13C NMR (100.6 MHz, CDCl3): δ 46.1, 91.2,
104.6, 112.3, 116.5, 117.2, 123.5, 124.3, 124.6, 126.3, 126.7, 129.2,
129.6, 130.5, 131.7, 133.2, 141.8, 155.2, 159.3, 161.6, 166.3, 190.2 ppm.
trans-2-(4-Chlorobenzoyl)-3-(4-chlorophenyl)-2,3-dihydro-4H-
furo[3,2-c]chromen-4-one (5e): White powder, m.p. 249–251 °C; IR
(KBr) νmax/cm−1: 2934, 2824, 1722, 1646, 1414, 1024, 758, 536; Anal.
calcd for C24H14Cl2O4: C, 65.92; H, 3.23; found: C, 65.80; H, 3.32%;
Experimental
Melting points were determined with an Electrothermal 9100
apparatus. Elemental analyses were performed using a Heraeus CHN-
O-Rapid Analyzer. Mass spectra were recorded on a Finnigan-MAT
8430 mass spectrometer operating at an ionisation potential of 70 eV.
IR spectra were recorded on a Shimadzu IR-470 spectrophotometer.
1H and 13C NMR spectra were recorded on a Bruker DRX-400 Avance
spectrometer in CDCl3 solution using tetramethylsilane (TMS) as
internal standard. 2-[2-(4-chlorophenyl)-2-oxoethyl]isoquinolinium
bromide 2 was prepared by the literature method.17 All other chemicals
used in this work were purchased from Fluka (Buchs, Switzerland) and
were used without further purification.
1
MS (m/z, %): 436 (10); H NMR (400 MHz, CDCl3): δ 4.88 (1H, d,
J = 5.2 Hz, H-3), 6.08 (1H, d, J = 5.2 Hz, H-2), 7.28 (2H, t, J = 7.4 Hz,
Ar-H), 7.29 (2H, d, J = 7.4 Hz, Ar-H), 7.36 (1H, t, J = 7.4 Hz, Ar-H),
7.38 (2H, d, J = 7.4 Hz, Ar-H), 7.52 (1H, d, J = 7.4 Hz, Ar-H), 7.83
(2H, d, J = 8 Hz, Ar-H), 7.90 (2H, d, J = 7.4 Hz, Ar-H) ppm; 13C NMR
(100.6 MHz, CDCl3): δ 48.3, 92.5, 105.3, 112.0, 116.4, 117.1, 123.1,
124.2, 129.3, 129.4, 130.5, 131.6, 133.3, 133.7, 135.1, 141.2, 155.4, 159.1,
166.14, 190.8 ppm.
General procedure
trans-2-(4-Chlorobenzoyl)-3-(2-fluorophenyl)-2,3-dihydro-4H-
furo[3,2-c]chromen-4-one (5f): Yellow powder, m.p. 219–221 °C;
IR (KBr) νmax/cm−1: 2930, 2853, 1713, 1644, 1450, 1402, 1024, 755,
574; Anal. calcd for C24H14ClFO4: C, 68.50; H, 3.35; found: C, 68.36;
H, 3.22%; MS (m/z, %): 420 (4); 1H NMR (400 MHz, CDCl3): δ 5.19
(1H, d, J = 5.4 Hz, H-3), 6.16 (1H, d, J = 5.4 Hz, H-2), 7.17–7.31 (3H,
m, Ar-H), 7.38 (1H, d, J = 7.4 Hz, Ar-H), 7.41 (1H, d, J = 7.4 Hz, Ar-
H), 7.43 (1H, t, J = 8.2 Hz, Ar-H), 7.52 (1H, d, J = 7.2 Hz, Ar-H), 7.66
(1H, d, J = 8.2 Hz, Ar-H), 7.80 (2H, d, J = 8.0 Hz, Ar-H), 7.94 (2H, d,
J = 8.0 Hz, Ar-H) ppm; 13C NMR (100.6 MHz, CDCl3): δ 43.1, 91.0,
103.7, 112.0, 116.3, 117.1, 123.1, 124.2, 124.9, 126.0, 126.1, 129.4, 129.6,
130.5, 131.7, 133.0, 141.1, 155.4, 159.5, 166.4, 166.4, 192.4 ppm.
trans-2-(4-Chlorobenzoyl)-3-(4-methoxyphenyl)-2,3-dihydro-4H-
furo[3,2-c]chromen-4-one (5g): White powder, m.p. 177–179 °C; IR
(KBr) νmax/cm−1: 1728, 1692, 1642, 1617, 1512, 1418, 1258, 1210, 1235,
1176, 1080, 1022, 935; Anal. calcd for C25H17ClO5: C, 69.37; H, 3.96;
found: C, 69.20; H, 3.85%; MS (m/z, %): 432 (8); 1H NMR (400 MHz,
CDCl3): δ 3.82 (3H, s, OMe), 5.33 (1H, d, J = 5.2 Hz, H-3), 6.09 (1H, d,
J = 5.2 Hz, H-2), 7.25 (2H, d, J = 8.4 Hz, Ar-H), 7.29 (2H, d, J = 8.4 Hz,
Ar-H), 7.33 (1H, t, J = 7.6 Hz, Ar-H), 7.40 (1H, d, J = 8.4 Hz, Ar-H),
7.49 (2H, t, J = 8.0 Hz, Ar-H), 7.56–7.65 (2H, m, Ar-H), 7.82 (1H, d, J =
7.6, 1.6 Hz, Ar-H), 7.90 (2H, d, J = 8.8 Hz, Ar-H) ppm; 13C NMR (100.6
MHz, CDCl3): δ 46.2, 55.7, 91.3, 104.8, 112.4, 116.8, 117.3, 123.6,
124.3, 124.5, 126.2, 126.6, 130.1, 131.8, 133.2, 141.6, 155.3, 159.4,
166.4, 190.3 ppm.
To
a magnetically stirred solution of 2-[2-(4-chlorophenyl)-2-
oxoethyl]isoquinolinium bromide (1 mmol), 4-hydroxycoumarin
(1 mmol) and aryl aldehyde (1 mmol) in H2O (10 mL) was added
choline hydroxide (0.0121 g, 0.1 mmol) in H2O (4 mL). The mixture
was then refluxed for 3 h. The solid product was filtered off and
recrystallised from ethanol to yield the pure product.
trans-2-(4-Chlorobenzoyl)-3-phenyl-2,3-dihydro-4H-furo[3,2-c]
chromen-4-one (5a): White powder, m.p. 201–203 °C; IR (KBr)
ν
max/cm−1: 2921, 2850, 1718, 1644, 1448, 1405, 1036, 756, 578; Anal.
calcd for C24H15ClO4: C, 71.56; H, 3.75; found: C, 71.43; H, 3.61%; MS
(m/z, %): 402 (5); 1H NMR (400 MHz, CDCl3): δ 4.84 (1H, d, J = 5.2
Hz, H-3), 6.14 (1H, d, J = 5.2 Hz, H-2), 7.22 (2H, t, J = 7.6 Hz, Ar-H),
7.33 (1H, t, J = 6.8 Hz, Ar-H), 7.37 (1H, t, J = 7.6 Hz, Ar-H), 7.38 (2H,
d, J = 6.8, Ar-H), 7.42 (2H, t, J = 6.8 Hz, Ar-H), 7.55 (1H, m, Ar-H),
7.85 (2H, d, J = 7.4 Hz, Ar-H), 7.84 (2H, d, J = 7.4 Hz, Ar-H) ppm;
13C NMR (100.6 MHz, CDCl3): δ 49.2, 92.5, 105.3, 112.1, 117.3, 123.1,
124.2, 126.6, 127.9, 128.3, 129.4, 130.5, 131.5, 133.1, 139.4, 141.1, 155.4,
159.2, 166.2, 191.1 ppm.
trans-2-(4-Chlorobenzoyl)-3-(2-nitrophenyl)-2,3-dihydro-4H-
furo[3,2-c]chromen-4-one (5b): White powder, m.p. 185–187 °C; IR
(KBr) νmax/cm−1: 2923, 2842, 1729, 1644, 1510, 1410, 1023, 745, 570;
Anal. calcd for C24H14ClNO6: C, 64.37; H, 3.15; N, 3.13; found: C,
64.26; H, 3.30; N, 3.22%; MS (m/z, %): 447 (3); 1H NMR (400 MHz,
CDCl3): δ 5.20 (1H, d, J = 5.2 Hz, H-3), 6.08 (1H, d, J = 5.2 Hz, H-2),
7.30 (2H, m, Ar-H), 7.33 (1H, t, J = 8.2 Hz, Ar-H), 7.42 (1H, d, J = 8 Hz,
Ar-H), 7.49 (1H, m, Ar-H), 7.58 (1H, d, J = 7.4 Hz, Ar-H), 7.66 (2H,
d, J = 8 Hz, Ar-H), 7.85 (1H, t, J = 7.4 Hz, Ar-H), 7.91 (2H, d, J = 8
Hz, Ar-H) 8.20 (1H, d, J = 7.6 Hz, Ar-H) ppm; 13C NMR (100.6 MHz,
CDCl3): δ 45.2, 91.3, 104.8, 112.2, 116.4, 117.3, 123.4, 124.2, 124.8,
126.5, 126.8, 129.3, 129.7, 130.6, 131.8, 133.1, 141.2, 155.3, 159.2, 161.7,
166.2, 191.1 ppm.
trans-2-(4-Chlorobenzoyl)-3-(4-fluorophenyl)-2,3-dihydro-4H-
furo[3,2-c]chromen-4-one (5h): Yellow powder, m.p. 226–228 °C; IR
(KBr) νmax/cm−1: 2924, 2836, 1724, 1646, 1412, 1024, 754, 534; Anal.
calcd for C24H14ClFO4: C, 68.50; H, 3.35; found: C, 68.38; H, 3.19%;
1
MS (m/z, %): 420 (5); H NMR (400 MHz, CDCl3): δ 4.88 (1H, d,
J = 5.2 Hz, H-3), 6.09 (1H, d, J =5.2 Hz, H-2), 7.29 (2H, t, J = 8.4 Hz,
Ar-H), 7.32 (2H, d, J = 8.4 Hz, Ar-H), 7.43 (1H, t, J = 8.4 Hz, Ar-H),
7.53 (2H, d, J = 8.4 Hz, Ar-H), 7.66 (1H, d, J = 8.4 Hz, Ar-H), 7.88 (2H,
d, J = 8.4 Hz, Ar-H), 7.90 (2H, d, J = 8 Hz, Ar-H) ppm; 13C NMR (100.6
trans-2-(4-Chlorobenzoyl)-3-(4-nitrophenyl)-2,3-dihydro-4H-
furo[3,2-c]chromen-4-one (5c): White powder, m.p. 181–183 °C; IR

658 JOURNAL OF CHEMICAL RESEARCH 2016
MHz, CDCl3): δ 48.3, 92.5, 105.1, 112.0, 116.4, 117.1, 123.1, 124.2,
129.3, 129.4, 130.5, 131.6, 133.1, 135.1, 141.2, 155.4, 159.5, 161.9, 166.4,
190.6 ppm.
Anal. calcd for C24H14BrClO4: C, 59.84; H, 2.93; found: C, 59.96; H,
3.08%; MS (m/z, %): 481 (4); 1H NMR (400 MHz, CDCl3): δ 4.86 (1H,
d, J = 5.4 Hz, H-3), 6.07 (1H, d, J = 5.4 Hz, H-2), 7.37 (2H, d, J = 7.4
Hz, Ar-H), 7.42 (2H, d, J = 8.2 Hz, Ar-H), 7.64 (1H, m, Ar-H), 7.66
(1H, d, J = 8 Hz, Ar-H), 7.88 (2H, d, J = 7.4 Hz, Ar-H), 7.88 (2H, d,
J = 8.2 Hz, Ar-H), 8.03 (2H, d, J = 8.2 Hz, Ar-H) ppm; 13C NMR (100.6
MHz, CDCl3): δ 49.1, 92.5, 105.3, 112.1, 117.1, 123.1, 124.3, 127.4, 12.5,
130.1, 130.5, 131.5, 132.9, 136.4, 138.2, 141.1, 155.5, 159.3, 166.1, 191.2
ppm.
trans-2-(4-Chlorobenzoyl)-3-(4-chloro-3-nitrophenyl)-2,3-
dihydro-4H-furo[3,2-c]chromen-4-one (5i): White powder, m.p.
235–237 °C; IR (KBr) νmax/cm−1: 2930, 2853, 1727, 1647, 1524, 1410,
747, 578; Anal. calcd for C24H13Cl2NO6: C, 59.77; H, 2.72; N, 2.90;
1
found: C, 59.61; H, 2.85; N, 3.04%; MS (m/z, %): 481 (5); H NMR
(400 MHz, CDCl3): δ 5.17 (1H, d, J = 5.6 Hz, H-3), 6.05 (1H, d,
J = 5.6 Hz, H-2), 7.36 (2H, m, Ar-H), 7.44 (1H, t, J = 8.2 Hz, Ar-
H), 7.54 (1H, d, J = 8.2 Hz, Ar-H), 7.58 (1H, m, Ar-H), 7.66 (1H, d,
J = 7.4 Hz, Ar-H), 7.69 (2H, d, J = 8.2 Hz, Ar-H), 7.85 (1H, t, J = 7.4 Hz,
Ar-H), 7.96 (2H, d, J = 8.2 Hz,) 7.98 (1H, d, J = 7.6 Hz, Ar-H) ppm;
13C NMR (100.6 MHz, CDCl3): δ 47.2, 91.9, 103.9, 111.6, 117.3, 123.6,
124.0, 126.9, 127.1, 127.5, 128.6, 129.5, 130.7, 131.3, 132.7, 133.6, 135.9,
141.5, 155.5, 159.5, 166.4, 190.3 ppm.
Received 30 July 2016; accepted 25 September 2016
Paper 1604224 doi: 10.3184/174751916X14757574219700
Published online: 24 October 2016
References
trans-[2-(4-Chlorobenzoyl)-4-oxo-2,3-dihydro-4H-furo[3,2-c]
chromen-3-yl]benzonitrile (5j): White powder, m.p. 194–196 °C; IR
(KBr) νmax/cm−1: 2935, 2854, 1725, 1645, 1527, 1410, 747, 575; Anal.
calcd for C25H14ClNO4: C, 70.18; H, 3.30; N, 3.27; found: C, 70.31; H,
3.19; N, 3.40%; MS (m/z, %): 427 (7); 1H NMR (400 MHz, CDCl3): δ
5.08 (1H, d, J = 5.4 Hz, H-3), 6.07 (1H, d, J = 5.4 Hz, H-2), 7.29 (2H,
m, Ar-H), 7.38 (1H, t, J = 8.4 Hz, Ar-H), 7.44 (1H, d, J = 8.4 Hz, Ar-
H), 7.47 (2H, d, J = 8.4 Hz, Ar-H), 7.69 (2H, d, J = 7.6 Hz, Ar-H), 7.81
(2H, d, J = 7.6 Hz, Ar-H), 7.93 (2H, d, J = 8.4 Hz, Ar-H) ppm; 13C NMR
(100.6 MHz, CDCl3): δ 48.3, 92.0, 104.3, 112.2, 117.2, 118.4, 123.1,
124.4, 128.5, 129.5, 130.6, 131.6, 132.2, 133.1, 133.4, 141.4, 155.4,
159.0, 166.3, 190.4 ppm.
trans-2-(4-Chlorobenzoyl)-3-(4-methylphenyl)-2,3-dihydro-4H-
furo[3,2-c]chromen-4-one (5k): White powder, m.p. 195–197 °C; IR
(KBr) νmax/cm−1: 2932, 2864, 1723, 1646, 1453, 1407, 1025, 753; Anal.
calcd for C25H17ClO4: C, 72.03; H, 4.11; found: C, 72.18; H, 4.00%; MS
(m/z, %): 416 (12); 1H NMR (400 MHz, CDCl3): δ 2.38 (3H, s, CH3),
4.78 (1H, d, J = 5.4 Hz, H-3), 6.12 (1H, d, J = 5.4 Hz, H-2), 7.37 (2H, d,
J = 7.2 Hz, Ar-H), 7.40 (2H, d, J = 7.2 Hz, Ar-H), 7.52 (2H, m, Ar-H),
7.63 (1H, t, J = 8.4 Hz, Ar-H), 7.65 (1H, d, J = 8.4 Hz, Ar-H), 7.85 (2H,
d, J = 7.6 Hz, Ar-H), 7.89 (2H, d, J = 7.6 Hz, Ar-H) ppm; 13C NMR
(100.6 MHz, CDCl3): δ 21.2, 49.0, 92.6, 105.4, 112.1, 117.1, 123.1,
124.2, 127.4, 129.4, 130.0, 130.4, 131.5, 132.9, 136.3, 138.1, 141.1,
155.4, 159.2, 166.1, 191.1 ppm.
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trans-2-(4-Chlorobenzoyl)-3-(4-bromophenyl)-2,3-dihydro-4H-
furo[3,2-c]chromen-4-one (5l): White powder, m.p. 189–191 °C;
IR (KBr) νmax/cm−1: 2917, 2821, 1718, 1645, 1405, 1028, 755, 538;