Alkanedisulfamic acid functionalized silica-coated magnetic nanoparticles: Preparation and catalytic investigation in synthesis of mono-, bis- and tris[bis(4-hydroxycoumarinyl)methanes]

Article abstract of DOI:10.1055/s-0034-1378667

Alkanedisulfamic acid-functionalized silica-coated magnetic nanoparticles (ADSA-MNPs) were prepared by a simple method and evaluated as efficient catalysts for the preparation of mono-, bis-, and tris[bis(4-hydroxycoumarinyl)methanes] through condensation

Full text of DOI:10.1055/s-0034-1378667

3180▌
PAPER
pAaplekr anedisulfamic Acid Functionalized Silica-Coated Magnetic Nanoparticles:
Preparation and Catalytic Investigation in Synthesis of Mono-, Bis- and
Tris[bis(4-hydroxycoumarinyl)methanes]
Mono-, Bis-, and Tris[bis(4-hydroxycoumarinyl)methanes]
Ali Reza Karimi,* Zahra Eftekhari, Marzie Karimi, Zeinab Dalirnasab
Department of Chemistry, Faculty of Science, Arak University, Arak 38156-8-8349, Iran
Fax +98(861)4173406; E-mail: a-karimi@araku.ac.ir
Received: 18.04.2014; Accepted after revision: 18.07.2014
they also suffer from some drawbacks, such as low yields,
Abstract: Alkanedisulfamic acid-functionalized silica-coated mag-
prolonged reaction times, the use of costly reagents or cat-
netic nanoparticles (ADSA-MNPs) were prepared by a simple
alysts, or the use of toxic organic solvents. The recovery
mono-, bis-, and tris[bis(4-hydroxycoumarinyl)methanes] through of the catalyst can also be a problem.
method and evaluated as efficient catalysts for the preparation of
condensation of 4-hydroxy-2H-coumarin-2-one with mono-, di-, or
Although the reaction of 4-hydroxycoumarin with
trialdehydes, respectively. The heterogeneous nanocatalyst was
readily recovered from the reaction mixture by using external mag-
net and was reused five times without significant loss of catalytic
activity.
1
1–19
monoaldehydes has been investigated,
there have
been no reports on reactions of 4-hydroxycoumarin with
di- or trialdehydes for the synthesis of bis- and tris[bis(4-
hydroxycoumarinyl)methanes], respectively. As a contin-
uation of our research on the preparation and catalytic in-
vestigation of new acid-functionalized magnetic
Key words: nanostructures, coumarins, heterogeneous catalysis,
condensation, catalyst supports
3
,20
nanoparticles,
we synthesized new alkanedisulfamic
acid magnetic nanoparticles (ADSA-MNPs) by direct re-
action of chlorosulfonic acid with diaminoalkylsilica-
coated magnetic nanoparticles (Scheme 1), and we used
these nanoparticles as a catalyst system for the synthesis
of mono-, bis-, and tris[bis(4-hydroxycoumarinyl)meth-
anes] by condensation of 4-hydroxycoumarin with mono-,
di-, or trialdehydes, respectively.
Acid-functionalized silica-coated magnetic nanoparticles
have recently emerged as attractive supports for immobi-
lization of homogeneous catalysts. Various acid-function-
alized silica-coated magnetic nanoparticles have been
prepared and used as efficient catalysts for a range of or-
ganic transformations, such as deprotection of benzalde-
1
hyde dimethylacetals and the synthesis of α-amino
nitriles;2 mono-, bis-, and tris[bis(6-aminopyrimidin-
3
4
yl)methanes]; quinolines; benzo[a]xanthenone deriva-
MeO
MeO
NH2
Si
N
5
6
H
tives; and aminoimidazopyridine skeletons.
3 4
Fe O
Fe3O4
MNP
CA
OMe
Coumarin derivatives have received considerable atten-
tion because of their useful pharmacological activities. 4-
Hydroxycoumarin derivatives have attracted particular at-
tention because of their useful biological and pharmaco-
CMNP
OSO3H
7
8
NH2
NHSO3H
logical properties, such as anticoagulant, spasmolytic,
3
Fe O
N
N
4
Fe3O4
H
SO3H
9
and rodenticidal activities. Coumarins in general, and
biscoumarins in particular, exhibit antifungal, anti-HIV,
anticancer, antithrombotic, antimicrobial, antioxidant
ClSO3H
ADSA-MNP
AEAP-MNP
1
0,11
Scheme 1 Preparation of alkanedisulfamic acid functionalized
urease-inhibitory, cytotoxic, and enzyme inhibitory ac- silica-coated magnetic nanoparticles (ADSA-MNPs)
1
2
tivities.13 As a result, the synthesis of this class of com-
pounds is very important.
To prepare the ADSA-MNPs, magnetic iron(III) oxide
The reaction of 4-hydroxycoumarin with aldehydes af- nanoparticles were treated with citric acid to give the cor-
fords the corresponding bis(4-hydroxycoumarinyl)meth- responding charged nanoparticles (CMNPs). The CMNPs
anes, a useful class of organic compounds. This reaction were then treated with N-[3-(triethoxysilyl)propyl]eth-
1
4
is catalyzed by ruthenium(III) chloride hydrate, piperi- ane-1,2-diamine (AEAPS) to give coated magnetic
dine,12 sulfated titania, iodine, or a poly(4-vinylpyri- nanoparticles (AEAP-MNPs), which were functionalized
15
16
1
7
dinium butylsulfonate)-supported catalyst. Although the by a simple one-step procedure through direct treatment
known procedures for the synthesis of corresponding with chlorosulfonic acid to give the ADSA-MNPs. The
bis(4-hydroxycoumarinyl)methanes have their merits, size of the nanoparticles was determined by scanning
electron microscopy (SEM). The SEM micrographs (Fig-
ure 1) showed that the ADSA-MNPs were spherical in
shape and that their average size was about 38 nm.
SYNTHESIS 2014, 46, 3180–3184
Advanced online publication: 21.08.2014
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DOI: 10.1055/s-0034-1378667; Art ID: ss-2014-z0250-op
Georg Thieme Verlag Stuttgart · New York
©

PAPER
Mono-, Bis-, and Tris[bis(4-hydroxycoumarinyl)methanes]
3181
were therefore obtained by using 0.1 g of ADSA-MNPs in
:1 ethanol–water at 60 °C with ultrasound irradiation.
4
Table 1 Optimization of Reaction for the Synthesis of Bis(4-hy-
droxy-2H-chromen-2-one) (3a) with Ultrasound Irradiation at 60 °Ca
Entry Catalyst
Solvent
Yield (%)
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
–
4:1 EtOH–H
2
O
10
45
75
95
81
75
30
85
55
20
40
20
22
38
80
70
ADSA-MNPs (0.03 g)
ADSA-MNPs (0.06 g)
ADSA-MNPs (0.10 g)
ADSA-MNPs (0.15 g)
ADSA-MNPs (0.10 g)
ADSA-MNPs (0.10 g)
ADSA-MNPs (0.10 g)
ADSA-MNPs (0.10 g)
ADSA-MNPs (0.10 g)
ADSA-MNPs (0.10 g)
MNPs (0.10 g)
4:1 EtOH–H O
2
4:1 EtOH–H O
2
4:1 EtOH–H O
2
4:1 EtOH–H O
2
Figure 1 SEM micrograph of ADSA-MNPs
EtOH
The thermal properties of ADSA-MNPs were analyzed by
thermal gravimetric analysis at 20–850 °C under nitrogen.
The primary weight loss at up to 160 °C was related to the
removal of physically adsorbed solvent. The rate of
weight loss between 160 and 500 °C was relatively slow,
showing that the ASDA-MNPs have a reasonably high
thermal stability at up to 500 °C. The maximum rate of
weight loss for these nanoparticles began at 500 °C. There
was a well-defined mass loss of 50% at between 160 and
H O
2
MeCN
DMF
1
1
1
1
1
1
THF
DMSO
4:1 EtOH–H O
2
7
00 °C, related to the breakdown of the sulfuric acid and
CMNPs (0.10 g)
4:1 EtOH–H O
2
alkylamine moieties.
AEAP-MNPs (0.10 g)
H SO (0.03 g)
4:1 EtOH–H O
2
The x-ray diffraction patterns of the ADSA-MNPs
showed that the cubic structure of the magnetite was well
preserved after introduction of the AEAPS and sulfuric
4:1 EtOH–H O
2
4
2
1
H SO (0.05 g)
4:1 EtOH–H O
2
4
2
2
2
acid functionality. The intensity of the 41.6° reflection
of the ADSA-MNPs decreased after introduction of the
sulfuric acid group.
a
Reaction conditions: 3-ClC H CHO (2a; 1 mmol), 4-hydroxy-2H-
6
4
coumarin-2-one (1a; 2 mmol), catalyst, solvent, 1 h, ultrasound.
To explore the use of ADSA-MNPs as a catalyst system,
we initially examined the preparation of 3,3′-[(3-chloro-
phenyl)methylene]bis(4-hydroxy-2H-chromen-2-one)
Table 2 Synthesis of Mono-, Bis-, and Tris[bis(4-hydroxycouma-
rinyl)methanes] Catalyzed by ADSA-MNPs at 60 °C with Ultrasound
Irradiation
(3a) by reaction of 3-chlorobenzaldehyde (2a; 1 mmol)
with 4-hydroxy-2H-coumarin-2-one (1; 2 mmol) under Entry Aldehyde Product Time Yield Mp
various conditions (Table 1).
Mp
(Lit. )
1
2
(h)
(%)
(°C)
We began by investigating the effects of various amounts
of ADSA-MNPs as catalyst in ethanol at 60 ºC under ul-
trasound irradiation. After 1 h, with 0, 0.03, 0.06, 0.1, and
92a
1
2
3
4
5
6
7
8
9
0
2a
2b
2c
2d
2e
2f
3a
3b
3c
3d
3e
3f
1
1
1
1
1
3
3
4
4
4
214–216
215
–
95
92
88
93
83
80
88b
85
83
225–227
212–214
200–203
226–228
>300
0.15 g of ADSA-MNPs, yields of 10, 45, 75, 95, and 81%,
210.5
193
228
–
respectively, of 3a were obtained (Table 1, entries 1–5).
The solvents were also found to play an important role in
this reaction. The use of ethanol, water, acetonitrile, N,N-
dimethylformamide, tetrahydrofuran, or dimethyl sulfox-
ide as the solvent gave poor yields (entries 6–11); the re-
action hardly proceeded in tetrahydrofuran. However, the
reaction in 4:1 ethanol–water afforded the product in high
yield with nearly complete conversion (entry 4). We
therefore selected 4:1 ethanol–water as the solvent for
subsequent investigations. The use of MNPs, CMNPs, or
AEAP-MNPs as heterogeneous catalysts or sulfuric acid
as a homogeneous catalyst gave low yields of the product
2g
2h
2i
3g
3h
3i
293–295
255–257
260–262
>300
–
–
–
1
2j
3j
–
a
Yields after successive recoveries and recycling of catalyst: 90, 88,
Yields for H SO catalyst 50% (0.03 g) and 55% (0.06 g).
(
Table 1, entries 12–16). The best reaction conditions 85, and 85%.
b
2
4
©
Georg Thieme Verlag Stuttgart · New York
Synthesis 2014, 46, 3180–3184

3182
A. R. Karimi et al.
PAPER
Next, we examined the reaction of a wide variety of In conclusion, we prepared ADSA-MNPs and examined
monoaldehydes 2a–e, dialdehydes 2f and 2g, and trialde- their catalytic activity. The results showed that this cata-
hydes 2h–j to establish the scope of this catalytic transfor- lyst system has some advantages. ADSA-MNPs were pre-
mation (Scheme 2).
pared in a simple manner by direct functionalization of
AEAP-MNPs with chlorosulfonic acid. The ADSA-
MNPs can be dispersed in solvents and can be isolated af-
ter use by using a magnet. In condensation reactions of 4-
hydroxy-2H-coumarin-2-one (1a) with aldehydes 2,
ADSA-MNPs showed short reaction times coupled with a
simple reaction procedure. The inexpensive and reusable
catalyst make this method one of the most efficient meth-
ods for the synthesis of mono-, bis-, and tris[(4-hydroxy-
coumarinyl)methanes].
The mono-, di- and tri-[bis(4-hydroxycoumarinyl) meth-
anes] synthesized by our method are listed in Table 2.
ADSA-MNPs as catalyst showed a high activity and could
be recovered and recycled four times without significant
loss of activity (Table 2, entry 1). The use of sulfuric acid
as catalyst in the synthesis of 3h favored side reactions
and gave a low yield of the product (entry 8).
R3
R2
OH
O
CHO
R1
R2
ADSA-MNPs
R1
+
O
EtOH–H O, 60 °C,
OH
O
OH
2
R3
2a R1 = H, R2 = Cl, R3 = H
1
b R = H, R = Br, R3 = H
1
2
2
2
2
2
O
O
O
1
2
3
c R = H, R = OH, R = H
1
2
3
d R = H, R = H, R = OH
3a–e
1
2
3
e R = H, R = H, R = H
O
O
O
O
OH
O
OH
ADSA-MNPs
+
CHO
OH
R
EtOH–H O, 60 °C,
O
2
OH
OH
O
1
2f R = 4-CHO
2
g R = 3-CHO
O
O
O
3f,g
O
OH
O
OAr
O
HO
O
O
ADSA-MNPs
N
N
O
OH
R
+
O
O
EtOH–H
2
O, 60 °C,
O
O
ArO
N
OAr
O
HO
N
N
1
6 4
2h Ar = 4-OHCC H
2
2
i Ar = 3-OHCC
j Ar = 3-MeO-4-OHCC
6 4
H
OH
O
N
O
6 3
H
R
R
OH
O
OH
O
O
O
3
3
3
b R = H
i R = H
j R = OMe
Scheme 2 Synthesis of mono-, bis- and tris[bis(4-hydroxycoumarinyl)methanes] 3a–i catalyzed by ADSA-MNPs
Synthesis 2014, 46, 3180–3184
© Georg Thieme Verlag Stuttgart · New York

PAPER
Mono-, Bis-, and Tris[bis(4-hydroxycoumarinyl)methanes]
3183
4
-Hydroxy-2H-coumarin-2-one (1), monoaldehydes 2a–e, tereph-
Anal. Calcd for C H BrO : C, 61.12; H, 3.08. Found: C, 61.45; H,
3.42.
2
5
15
6
thalaldehyde (2f), isophthalaldehyde (2g), FeCl , AEAPS, cyanuric
3
chloride, and the various solvents were used without further purifi-
3
,3′-[(3-Hydroxyphenyl)methylene]bis(4-hydroxy-2H-
cation. Fe O nanoparticles (MNP) and citric acid-modified
3
4
12
chromen-2-one) (3c)
nanoparticles (CMNPs) were prepared according to the procedure
1
2
2
3,24
White solid; yield: 0.393 g (92%); mp 212–214 °C (Lit. 210.5 °C).
IR (KBr): 3200, 2870, 2800, 1666, 1620, 1560, 1502, 1478 cm–1.
described in the literature.
Trialdehydes 2h–j were also pre-
25
pared according to a procedure described in the literature. Sonica-
tion was performed in a Struers Metason 200 HT ultrasonic cleaner
at a frequency of 50–60 kHz and an output power of 140 W. The
products were characterized by elemental analysis and by IR, H
NMR, and C NMR spectroscopy. FTIR spectra were recorded by
1
H NMR (300 MHz, DMSO-d ): δ = 5.45 (br s, 3 H, OH), 6.28 (s, 1
6
H, CHmethine), 7.13–7.15 (m, 2 H, Harom), 7.24–7.33 (m, 6 H, Harom),
1
7.57 (t, J = 2.0 Hz, 2 H, Harom), 7.85 (d, J = 2.0 Hz, 2 H, Harom).
1
3
1
using a Unicom Galaxy Series FTIR 5000 spectrophotometer. H
3
,3′-[(4-Hydroxyphenyl)methylene]bis(4-hydroxy-2H-
1
3
12
and C NMR spectra were recorded on a Bruker Avance 300 MHz
spectrometer at 300 and 75 MHz, respectively. Mass spectra were
recorded on a Shimadzu QP 1100 EX mass spectrometer operated
in the EI mode. Elemental analyses were performed by using Vario
EL III elemental analyzer.
chromen-2-one) (3d)
12
White solid; yield: 0.376 g (88%); mp 200–203 °C (Lit. 193 °C).
IR (KBr): 3272, 2860, 2801, 1662, 1614, 1580, 1452, 954 cm–1.
Anal. Calcd for C H O : C, 70.09; H, 3.76. Found: C, 70.42; H,
25 16
7
4.05.
{
[N-(2-Aminoethyl)-3-amino]propyl}silica-Coated Magnetic
Nanoparticles (AEAP-MNPs)
3,3′-(Phenylmethylene)bis(4-hydroxy-2H-chromen-2-one)
1
2
CMNPs (1.5 g) were dispersed in EtOH–H O (1:1; 250 mL) and
sonicated for 30 min to ensure dispersion. AEAPS (2.5 mL) was
added with mechanical stirring, and the mixture was agitated at
4
(3e)
2
12
White solid; yield: 0.383 g (93%); mp 226–228 °C (Lit. 228 °C).
IR (KBr): 3228, 2885, 2807, 1672, 1604, 1560, 1491, 748 cm–1.
0 °C for 4 h. The black precipitate was isolated by magnetic decan-
Anal. Calcd for C H O : C, 72.81; H, 3.91. Found: C, 73.12; H,
25
16
6
tation, washed with deionized H O and EtOH, and dried at r.t.
2
4.26.
Alkanedisulfamic Acid-Functionalized Silica-Coated Magnetic
Nanoparticles (ADSA-MNPs)
The prepared AEAP-MNPs were placed in a two-necked flask
equipped with a constant-pressure dropping funnel and a tube for
removing the HCl gas that formed by conducting it to an adsorbent
3
,3′,3′′,3′′′-[1,4-Phenylenedi(methanetriyl)]tetrakis(4-hydroxy-
2
H-chromen-2-one) (3f)
White solid; yield: 0.619 g (83%); mp >300 °C.
–
1
IR (KBr): 3274, 2889, 2857, 1660, 1618, 1586, 1520, 1483 cm .
solution. ClSO H (1.5 mL) was added dropwise over 30 min at r.t.,
1
3
H NMR (300 MHz, DMSO-d ): δ = 5.65 (br s, 4 H, OH), 6.36 (s, 2
6
and the mixture was subjected to slow mechanical stirring. HCl gas
immediately evolved from the reaction vessel. The mixture was
then shaken well for 30 min. The ADSA-MNPs were washed with
H, CHmethine), 7.07 (s, 4 H, Harom) 7.34–7.41 (m, 8 H, Harom), 7.63 (t,
J = 2.0 Hz, 4 H, Harom), 7.94 (d, J = 2.0 Hz, 4 H, Harom).
MS (EI): m/z = 746 [M+].
acetone and distilled water to remove excess ClSO H and then dried
3
in an oven at 60 °C for 6 h.
Anal. Calcd for C H O : C, 70.78; H, 3.51. Found: C, 71.04; H,
4
4
26 12
3
.86.
Mono-, Bis-, and Tris[bis(4-hydroxycoumarinyl)methanes]
(3a–j); General Procedure
3
,3′,3′′,3′′′-[1,3-Phenylenedi(methanetriyl)]tetrakis(4-hydroxy-
A mixture of monoaldehyde 2a–e, dialdehyde 2f–g, or trialdehyde
h–j (1 mmol), 4-hydroxy-2H-coumarin-2-one 1 (2.2 mmol for 2a–e,
mmol for 2f and 2g, or 7 mmol for 2h–j) and ADSA-MNPs (0.1
g for 2a–e, 0.12 g for 2f or 2g, or 0.15 g for 2h–j) in 4:1 EtOH–H O
2
H-chromen-2-one) (3g)
2
5
White solid; yield: 0.597 g (80%); mp 293–295 °C.
–1
IR (KBr): 3280, 2982, 2800, 1660, 1620, 1602, 1566, 1494, 914 cm .
2
1
(
10 mL) was exposed to ultrasound irradiation at 60 °C for the ap-
propriate time (see Table 2). When the reaction was complete
TLC), the ADSA-MNPs were removed by using an applied exter-
H NMR (300 MHz, DMSO-d ): δ = 4.46 (br s, 4 H, OH), 6.27 (s, 2
6
H, CHmethine), 6.92–6.94 (m, 3 H, Harom), 7.09 (t, J = 2.0 Hz, 1 H,
Harom), 7.19–7.23 (m, 8 H, J = 2.0 Hz, Harom), 7.53 (t, J = 2.0 Hz, 4
H, Harom), 7.67 (d, J = 1.8 Hz, 4 H, Harom).
13
(
nal magnetic field. The solution was concentrated then left to evap-
orate slowly. An EtOH–H O (5:1) mixture was added, and the
2
C NMR (75 MHz, DMSO-d ): δ = 35.78, 115.78, 116.34, 117.22,
18.81, 123.57, 123.73, 125.11, 127.99, 128.79, 131.82, 132.69,
38.88, 151.85, 164.75.
6
resulting solid product was collected by filtration and washed with
1
1
EtOH–H O (5:1) to remove excess coumarin 1.
2
3
,3′-[(3-Chlorophenyl)methylene]bis(4-hydroxy-2H-chromen-
Anal. Calcd for C H O : C, 70.78; H, 3.51. Found: C, 71.11; H,
44 26 12
3.89.
1
2
2
-one) (3a)
12
White solid; yield: 0.41 g (92%); mp 214–216 °C (Lit. 215 °C).
–
1
3,3′,3′′,3′′′,3′′′′,3′′′′′-[1,3,5-Triazine-2,4,6-triyltris(oxy-4,1-
phenylenemethanetriyl)]hexakis(4-hydroxy-2H-chromen-2-
one) (3h)
IR (KBr): 3272, 2889, 2825, 1668, 1620, 1562, 1489, 1450, 906 cm .
Anal. Calcd for C H ClO : C, 67.20; H, 3.38. Found: C, 67.41; H,
2
5
15
6
3.52.
White solid; yield: 1.19 g (88%); mp 255–257 °C.
–
1
IR (KBr): 3270, 2980, 2878, 1660, 1620, 1562, 1475, 910 cm .
3
,3′-[(3-Bromophenyl)methylene]bis(4-hydroxy-2H-chromen-
1
2
-one) (3b)
H NMR (300 MHz, DMSO-d ): δ = 4.80 (br s, 6 H, OH), 6.33 (s, 3
6
White solid; yield: 0.465 g (95%); mp 225–227 °C.
H, CHmethine), 6.92–7.03 (m, 9 H, Harom), 7.24–7.34 (m, 15 H, Harom),
–
1
7.58 (t, J = 1.8 Hz, 6 H, Harom), 7.86 (d, J = 1.7 Hz, 6 H, Harom).
IR (KBr): 3267, 2892, 2804, 1662, 1606, 1564, 1452, 910 cm .
1
3
1
C NMR (75 MHz, DMSO-d ): δ = 35.94, 115.67, 116.35, 118.58,
H NMR (300 MHz, DMSO-d ): δ = 5.43 (br s, 2 H, OH), 6.31 (s, 1
6
6
1
1
23.17, 123.93, 128.78, 130.51, 131.41, 132.71, 140.56, 142.59,
44.59, 152.353, 164.59.
H, CHmethine), 7.17 (q, J = 2.0 Hz, 2 H, Harom), 7.27–7.35 (m, 6 H,
Harom), 7.59 (t, J = 2.0 Hz, 2 H, Harom), 7.9 (d, J = 2.0 Hz, 2 H, Harom).
Anal. Calcd for C H N O : C, 68.87; H, 3.33; N, 3.09. Found: C,
7
8
45
3
21
69.09; H, 3.65; N, 3.41.
©
Georg Thieme Verlag Stuttgart · New York
Synthesis 2014, 46, 3180–3184

3184
A. R. Karimi et al.
PAPER
3
,3′,3′′,3′′′,3′′′′,3′′′′′-[1,3,5-Triazine-2,4,6-triyltris(oxy-3,1-
(2) Kassaee, M. Z.; Masrouri, H.; Movahedi, F. Appl. Catal. A.
2011, 395, 28.
phenylenemethanetriyl)]hexakis(4-hydroxy-2H-chromen-2-
one) (3i)
(
3) Karimi, A. R.; Dalirnasab, Z.; Karimi, M.; Bagherian, F.
White solid; yield: 1.15 g (85%); mp 260–262 °C.
Synthesis 2013, 45, 3300.
(4) Sheykhan, M.; Ma’mani, L.; Ebrahimi, A.; Heydari, A.
–
1
IR (KBr): 3378, 2933, 2887, 1664, 1618, 1566, 1487, 950 cm .
1
J. Mol. Catal. A: Chem. 2011, 335, 253.
H NMR (300 MHz, DMSO-d ): δ = 5.35 (br s, 6 H, OH), 6.33 (s, 3
6
(
(
(
(
5) Saadatjoo, N.; Golshekan, M.; Shariati, Sh.; Kefayati, H.;
Azizi, P. J. Mol. Catal. A: Chem. 2013, 377, 173.
6) Rostamnia, S.; Lamei, K.; Mohammadquli, M.; Sheykhan,
M.; Heydari, A. Tetrahedron Lett. 2012, 53, 5257.
7) Nagashima, R.; O’Reilly, R.; Levy, G. Clin. Pharmacol.
Ther. 1969, 1, 22.
H, CHmethine), 7.07–7.09 (m, 6 H, Harom), 7.17–7.20 (m, 6 H, Harom),
7.27–7.33 (m, 12 H, Harom), 7.56 (t, J = 2.0 Hz, 6 H, Harom), 7.89 (d,
J = 2.0 Hz, 6 H, Harom).
3
C NMR (75 MHz, DMSO-d ): δ = 35.69, 115.70, 116.35, 118.72,
6
118.92, 120.92, 122.33, 123.35, 124.05, 127.76, 131.00, 131.48,
132.71, 138.75, 149.10, 152.31, 166.59.
8) Stacchino, C.; Spanò, R.; Pettiti, A. Boll. Chim. Farm. 1983,
122, 158.
Anal. Calcd for C H N O : C, 68.87; H, 3.33; N, 3.09. Found: C,
7
8
45
3
21
6
9.12; H, 3.62; N, 3.44.
(9) McIntyre, J. S.; Knight, A. R. US 3511856, 1970.
10) Jung, J. C.; Park, O. S. Molecules 2009, 14, 4790.
11) Su, C.-X.; Mouscadet, J.-F.; Chiang, C.-C.; Tsai, H.-J.; Hsu,
L.-Y. Chem. Pharm. Bull. 2006, 54, 682.
(
(
3,3′,3′′,3′′′,3′′′′,3′′′′′-{1,3,5-Triazine-2,4,6-triyltris[oxy(3-
methoxy-4,1-phenylene)methanetriyl]}hexakis(4-hydroxy-2H-
chromen-2-one) (3j)
(
12) Khan, K. M.; Iqbal, S.; Lodhi, M. A.; Maharvi, G. M.; Zia-
Ullah Choudhary, M. I.; Atta-ur-Rahman; Perveen, S.
Bioorg. Med. Chem. 2004, 12, 1963.
White solid; yield: 1.20 g (83%); mp >300 °C.
–
1
IR (KBr): 3416, 3078, 2935, 1664, 1614, 1566, 1454, 927 cm .
1
H NMR (300 MHz, DMSO-d ): δ = 3.55 (s, 9 H, HOCH3), 4.3 (br s,
(13) Choudhary, M.; Fatima, N.; Khan, K. M.; Jalil, S.; Iqbal, S.;
Atta-ur-Rahman Bioorg. Med. Chem. 2006, 14, 8066.
(14) Tabatabaeian, K.; Heidari, H.; Khorshidi, A. R.;
Mamaghani, M.; Mahmoodi, N. O. J. Serb. Chem. Soc.
2012, 77, 407.
6
6
H, OH), 6.31 (s, 3 H, CHmethine), 6.74–6.88 (m, 6 H, Harom), 7.27–
7.32 (m, 15 H, Harom), 7.54 (t, J = 2.0 Hz, 6 H, Harom), 7.88 (d,
J = 2.0 Hz, 6 H, Harom).
3
C NMR (75 MHz, DMSO-d ): δ = 36.10, 55.99, 103.67, 111.65,
6
(
15) Karmakar, B.; Nayak, A.; Banerji, J. Tetrahedron Lett. 2012,
3, 4343.
1
1
15.67, 116.33, 118.98, 123.16, 124.07, 131.33, 132.66, 140.02,
41.32, 152.33, 152.35, 158.32, 161.32, 164.55.
5
(
16) Zareai, Z.; Khoobi, M.; Ramazani, A.; Foroumadi, A. R.;
Souldozi, A.; Ślepokura, K.; Lis, T.; Shafiee, A.
Tetrahedron 2012, 68, 6721.
Anal. Calcd for C H N O : C, 67.08; H, 3.54; N, 2.90. Found: C,
8
1
51
3
24
67.35; H, 3.86; N, 3.23.
(17) Boroujeni, K. P.; Ghasemi, P. Catal. Commun. 2013, 37, 50.
(18) Devi, I.; Bhuyan, P. J. Tetrahedron Lett. 2005, 46, 5727.
(19) Tavakoli-Hoseini, N.; Heravi, M. M.; Bamoharram, F. F.;
Davoodnia, A.; Ghassemzadeh, M. Bull. Korean Chem. Soc.
2011, 163, 122.
Acknowledgment
We gratefully acknowledge financial support from the Research
Council of Arak University.
(
20) Karimi, A. R.; Dalirnasab, Z.; Karimi, M. Synthesis 2014,
4
6, 917.
Supporting Information for this article is available online
(21) Ghosh, S.; Badruddoza, A. Z. M.; Uddin, M. S.; Hidajat, K.
J. Colloid Interface Sci. 2011, 354, 483.
(22) Tsukimura, K.; Sasaki, S.; Kimizuka, N. Jpn. J. Appl. Phys.
at
http://www.thieme-connect.com/products/ejournals/journal/
1
0.1055/s-00000084.SunpfgIpi
o
nr
i
o
1
997, 36, 3609.
(
(
(
23) Peng, Z. G.; Hidajat, K.; Uddin, M. S. J. Colloid Interface
Sci. 2004, 271, 277.
24) Chen, F. H.; Gao, Q.; Ni, J. Z. Nanotechnology 2008, 19,
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