Choline chloride and itaconic acid-based deep eutectic solvent as an efficient and reusable medium for the preparation of 13-aryl-5H-dibenzo[b,i]xanthene-5,7,12,14(13H)-tetraones

Article abstract of DOI:10.1007/s00706-015-1571-z

Choline chloride and itaconic acid-based deep eutectic solvent has been identified as an effective catalyst and reaction medium for synthesis of 13-aryl-5H-dibenzo[b,i]xanthene-5,7,12,14(13H)-tetraones by condensation of 2-hydroxynaphthalene-1,4-dione wit

Full text of DOI:10.1007/s00706-015-1571-z

Monatsh Chem
DOI 10.1007/s00706-015-1571-z
ORIGINAL PAPER
Choline chloride and itaconic acid-based deep eutectic solvent
as an efficient and reusable medium for the preparation
of 13-aryl-5H-dibenzo[b,i]xanthene-5,7,12,14(13H)-tetraones
Peng Liu1 Jian-Wu Hao1 Shao-Juan Liang1 Guang-Li Liang1 Jin-Yu Wang1 Zhan-Hui Zhang1
•
•
•
•
•
Received: 24 July 2015 / Accepted: 8 September 2015
Ó Springer-Verlag Wien 2015
Abstract Choline chloride and itaconic acid-based deep
eutectic solvent has been identified as an effective catalyst
and reaction medium for synthesis of 13-aryl-5H-
dibenzo[b,i]xanthene-5,7,12,14(13H)-tetraones by conden-
sation of 2-hydroxynaphthalene-1,4-dione with various
aldehydes. The reaction conditions are mild and environ-
mentally friendly.
various well-designed methodologies have been developed
to assemble these interesting scaffolds. In particular, the
construction of 13-aryl-5H-dibenzo[b,i]xanthene-5,7,12,14-
(13H)-tetraones has been conventionally accomplished by
reaction of aldehydes with 2-hydroxynaphthalene-1,4-
dione in the presence of various catalysts, such as poly(4-
vinylpyridinium) hydrogensulfate [9], p-toluenesulfonic
acid [10, 11], starch sulphate [12], phosphoric acid supported
on alumina (H3PO4/Al2O3) [13], N-sulfonic acid poly(4-
vinylpyridinium) hydrogensulfate [14], and ionic liquids [15–
20]. Due to their manifold applications, the development of a
novel methodology for synthesis of xanthenes will be a
valuable contribution to this class heterocycles.
Graphical abstract
O
O
O
R
O
O
O
OH
ChCl/itaconic acid
80 oC
+
2
RCHO
O
In recent years, a new family of solvents, so-called deep
eutectic solvents (DESs) or low melting mixtures (LMMs),
has been emerged in organic transformations [21] and other
research fields as reviewed in the literatures [22–25]. They are
prepared by mixing phosphonium or quaternary ammonium
salt such as choline chloride (ChCl) with hydrogen-bond
donors such as acids, alcohols, amines, or carbohydrates
without any further purification steps, which form a liquid by
hydrogen-bond interactions. The properties of DESs are sim-
ilar to that of conventional ionic liquids in terms of
undetectable vapour pressure, wide liquid temperature range,
good solubility for many organic or inorganic compounds, and
the feasibility for designing. The ease of preparation, avail-
ability, cost effectiveness, stability, less toxicity, and
biodegradability make these DESs versatile alternatives to
ionic liquids. In view of some previous works [26–38] and our
recent research programme on the development of novel and
environmentally benign synthetic methodologies [39–45],
herein we report ChCl/itaconic acid as reaction medium and
catalyst for the synthesis of 13-aryl-5H-dibenzo[b,i]xanthene-
5,7,12,14(13H)-tetraones by condensation of 2-hydroxy-
naphthalene-1,4-dione with aldehydes (Scheme 1).
Keywords Deep eutectic solvents Á
Low melting mixtures Á Choline chloride/itaconic acid Á
Xanthene derivatives
Introduction
Xanthene and their derivatives are an important class of
heterocyclic compounds that exhibit broad spectra of
pharmaceutical and biological properties, such as antimi-
crobial [1], antiproliferative [2], antibacterial [3], and
antioxidant activity [4]. Xanthenes can also be used in the
preparation of stable laser dyes [5], fluorescent sensor [6,
7], and protein labelling fluorophores [8]. Consequently,
& Zhan-Hui Zhang
zhanhui@126.com
1
College of Chemistry and Material Science, Hebei Normal
University, Shijiazhuang 050024, China
123

P. Liu et al.
Scheme 1
O
O
O
O
R
O
O
OH
ChCl/itaconic acid
80 oC
+
2
RCHO
O
1
2
3
Scheme 2
O
H O
O
N
80 oC
1 h
HO
N
+
Cl
OH
HO
Cl
O
HO
H O
O
Choline chloride
Itaconic acid
Deep eutectic solvent
Results and discussion
The preparation of ChCl/itaconic acid-based DES was
performed by mixing ChCl and itaconic acid at 80 °C
until
a homogenous colourless liquid was formed
(Scheme 2). Then, it was cooled to room temperature and
can be directly used without any further purification. This
method gave DES with 100 % atom economy since it
completely forms a eutectic mixture with no by-product
formation.
Figure 1 shows the FT-IR spectra of pure ChCl, itaconic
acid versus DES consisting of ChCl and itaconic acid. The
characteristic peaks of itaconic acid at 1708, 1438, 1310,
1230, 1218, and 1129 cm-1 and peaks of ChCl at 1632,
1478, 1406, 1092, and 949 cm-1 can also be observed in
the DES. The peaks of OH groups from ChCl and itaconic
acid are shifted and broaden due to in the formation of
H-bonding in the DES [46].
The thermal stability of ChCl/itaconic acid was inves-
tigated by thermogravimetric analysis (TGA) in the N2
atmosphere, which shows four-stage decomposition, (1)
below 162 °C, (2) between 162 and 216 °C, (3) between
216 and 315 °C, and (4) above 350 °C (Fig. 2). The first
region, which occurred below 162 °C, displays a mass loss
that is attributable to the removal of water. The weight loss
of DES appears about 29 % at 162–216 °C which is con-
tributed to the thermal decomposition of ChCl. And a
significant mass loss of above 56 % appears between 216
and 315 °C, which may be associated with the thermal
decomposition of itaconic acid. Thus, the synthesized DES
was stable up to 162 °C, confirming that it could be safely
used in organic reactions under 162 °C.
Fig. 1 FTIR spectra of pure ChCl, itaconic acid, and ChCl/itaconic
acid
Then, we chose the reaction between 2-hydroxynaph-
thalene-1,4-dione with benzaldehyde as the prototype to
synthesize 13-phenyl-5H-dibenzo[b,i]xanthene-5,7,12,14-
123

Choline chloride and itaconic acid-based deep eutectic solvent as an efficient and reusable…
(13H)-tetraone by using different deep eutectic solvents. As
shown in Table 1, no desired product was obtained under
solvent-free condition at 100 °C (Table 1, entry 1). Some
DESs such as ChCl/ZnCl2, ChCl/FeCl3, ChCl/SnCl2, ChCl/
glycerol, ChCl/urea, D-(-)-fructose/DMU, glucose/DMU/
NH4Cl were tested and only a trace amount of product was
detected (Table 1, entries 2–9). Considering this reaction
works well under acidic conditions, some acidic media were
investigated in order to obtain satisfactory results. To our
great delight, a significant improvement of the yields was
observed when the reaction was conducted in DESs such as
ChCl/L-(?)-tartaric acid, ChCl/citric acid, ChCl/oxalic acid
(entries 10–14). Further study showed that the yield could
be increased to as high as 93 % when ChCl/itaconic acid
was used (Table 1, entry 18). To optimize the reaction
temperature, the model reaction was carried out at different
Fig. 2 Thermogravimetric analysis of synthesized ChCl/itaconic acid
Table 1 Optimization of the
reaction conditions
Entry
DES
Temp/°C
Yield/%a
1
No
100
80
80
80
80
80
80
80
80
100
80
85
88
80
50
60
70
80
90
80
80
80
80
80
80
0
2
ChCl/FeCl3 (1:2)
Trace
3
ChCl/SnCl2 (1:2)
Trace
4
ChCl/ZnCl2 (1:2)
Trace
5
ChCl/glycerol (1:2)
Trace
6
ChCl/urea (1:2)
Trace
7
D-(-)-Fructose/DMU (70:30)b
Maltose/DMU/NH4Cl (50:40:10)b
Glucose/DMU/NH4Cl (60:30:10)b
Citric acid/urea/mannitol (30:20:60)b
ChCl/L-(?)-tartaric acid (2:1)
ChCl/citric acid (1:2)
Trace
8
Trace
9
Trace
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24c
25d
10
35
43
ChCl/oxalic acid (1:1)
52
ChCl/p-TsOH acid (1:1)
ChCl/itaconic acid (1:1)
ChCl/itaconic acid (1:1)
ChCl/itaconic acid (1:1)
ChCl/itaconic acid (1:1)
ChCl/itaconic acid (1:1)
ChCl/itaconic acid (1:1) 0.25 g
ChCl/itaconic acid (1:1) 0.50 g
ChCl/itaconic acid (1:1) 0.75 g
ChCl/itaconic acid (1:1) 1.50 g
ChCl/itaconic acid (1:1)
ChCl/itaconic acid (1:1)
85
18
34
80
93
93
12
36
81
93
92
92, 90, 89, 87, 85
Reaction conditions: benzaldehyde (1 mmol), 2-hydroxynaphthalene-1,4-dione (2 mmol), solvent (1.0 g),
2 h
a
Isolated yields
b
The ratio is given in weight %
c
The reaction was carried out in 50 mmol scale
d
ChCl/itaconic acid was reused for 5 times
123

P. Liu et al.
Table 2 Synthesis of 13-aryl-5H-dibenzo[b,i]xanthene-5,7,12,14(13H)-tetraones in ChCl/itaconic acids
Entry
Aldehyde
Product
Time/h
Yield/%a
m.p./°C
Found
Reported
1
PhCHO
3a
3b
3c
3d
3e
3f
2.0
2.0
2.0
2.0
2.0
3.0
3.0
3.0
3.0
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
2.0
3.0
3.0
3.0
93
91
92
90
91
89
88
92
86
94
90
91
92
91
89
90
91
92
90
88
87
89
89
307–308
303–305
218–220
263–264
[330
305–307 [16]
304–307 [10]
2
4-MeC6H4CHO
3
2-HOC6H4CHO
2-MeOC6H4CHO
4-MeOC6H4CHO
3-MeO-4-HOC6H3CHO
3,4-(MeO)2C6H3CHO
3-C6H4OC6H4CHO
4-(CH3)3CC6H4CHO
2-FC6H4CHO
4
262–265 [16]
5
[320 [14]
6
310–312
294–295
273–275
298–300
271–273
271–272
284–207
[330
7
3g
3h
3i
[300 [16]
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
a
3j
4-FC6H4CHO
3k
3l
270–272 [16]
283–285 [16]
[320 [14]
2-BrC6H4CHO
4-BrC6H4CHO
3m
3n
3o
3p
3q
3r
3s
2-ClC6H4CHO
306–308
280–282
[330
307–309 [10]
282–284 [16]
[320 [14]
3-ClC6H4CHO
4-ClC6H4CHO
2-NO2C6H4CHO
3-NO2C6H4CHO
4-NO2C6H4CHO
3-Br-5-Cl-2-HOC6H2CHO
2-Thiophenecarbaldehyde
1-Naphthaldehyde
Terephthalaldehyde
273–277
[330
340–342 [13]
[330
[320 [14]
3t
254–256
263–265
319–324
286–289
3u
3v
3w
Isolated yield
O
O
O
Scheme 3
CHO
O
O
OH
O
O
O
O
ChCl/itaconic acid
80 oC, 3 h, 80%
+
4
CHO
O
O
O
3x
temperature. It was found that the expected product was
obtained from 18 to 93 % yields when the reaction tem-
perature was raised from 50 to 80 °C (Table 1, entries
15–18). However, no increase in the yield of product was
observed when the reaction temperature was raised from 80
to 90 °C. By screening different amount of ChCl/itaconic
acid, it was found that product was formed in yields ranging
from 12 to 93 % (Table 1, entries 19–23). The best amount
123

Choline chloride and itaconic acid-based deep eutectic solvent as an efficient and reusable…
Scheme 4
CHO
Ph
O
OH
ChCl/itaconic acid
+
2
80 oC, 2.0 h, 92%
4
6
O
O
CHO
O
Ph
O
ChCl/itaconic acid
80 oC, 1.5 h, 95%
2
+
O
5
7
of DES was 1.0 g. Further increase of the DES did not affect
the yield (Table 1, entry 23).
above conditions when aliphatic aldehydes such as
acetaldehyde, n-propionaldehyde, 3-methylbutyraldehyde,
and cyclohexanecarbaldehyde were used as substrates.
Furthermore, this reaction was further applied for the
synthesis of (1,4-phenylene)bis(5H-dibenzo[b,i]xanthene-
5,7,12,14(13H)-tetraone (3x) by the reaction of p-phthal-
aldehyde and 4 equiv. of 2-hydroxynaphthalene-1,4-dione
under similar conditions in good yield (Scheme 3). To
further expand the potential of this approach as a tool for
the construction of xanthenes, we investigated the reaction
of benzaldehyde with b-naphthol (4) or dimedone (5). As
shown in Scheme 4, benzaldehyde could react smoothly
with b-naphthol or dimedone to give the desired 14-phe-
nyl-14H-dibenzo[a,j]xanthene (6) [27] and 3,3,6,6-
tetramethyl-9-phenyl-3,4,5,6,7,9-hexahydro-1H-xanthene-
1,8(2H)-dione (7) [47] in high yields.
In order to demonstrate the practical applicability of this
process, the model reaction was carried out in a larger scale
(50 mmol of benzaldehyde, 100 mmol of 2-hydroxynaph-
thalene-1,4-dione in 50 g ChCl/itaconic acid). The reaction
was completed in 2 h with 91 % yield (Table 1, entry 24).
On the same scale, the recyclability of DES was also
explored for the selected model reaction. After completion
of the reaction, the mixture was cooled to room tempera-
ture and water was added to the reaction mixture. The solid
product was isolated by filtration and washed with water.
The DES was dissolved in water. The water containing
DES was evaporated under reduced pressure and DES was
recovered and reused. The recovered DES was reused for
five times without a significant reduction in the yield
(Table 1, entry 25).
After optimizing the reaction conditions, to test the
scope and generality of this protocol, a series of substituted
aromatic aldehydes were investigated and the results were
summarized in Table 2. Various aromatic aldehydes bear-
ing electron-neutral, electron-rich, or electron-poor groups
reacted with 2-hydroxynaphthalene-1,4-dione to afford the
desired products in high yields. The product yields were
only slightly affected by the location of the substituents (on
ortho-, meta-, or para-positions of the benzene ring)
(Table 2, entries 2–20). Much to our satisfaction, halo-
substituted aldehydes were successfully converted into
target products, which allowed for easy further function-
alization. Furthermore, the acid-sensitive heterocyclic
aldehyde such as 2-thiophenecarbaldehyde was found to be
suitable for this transformation and afforded the corre-
sponding product in 87 % yield (Table 2, entry 21). It is
noteworthy that the system also worked well for sterically
hindered substrate such as 1-naphthaldehyde (Table 2,
entry 22). Unfortunately, no product was observed under
Conclusion
In summary, the present protocol introduces ChCl/itaconic
acid as an efficient catalyst and reaction medium for the
synthesis of 13-aryl-5H-dibenzo[b,i]xanthene-5,7,12,14
(13H)-tetraones by condensation of 2-hydroxynaphthalene-
1,4-dione with various aldehydes. The present protocol
offers some advantages such as cleaner reaction profile,
metal-free, high yields, simple workup procedure, and
avoidance of the use of toxic organic solvents and addi-
tional Brønsted or Lewis acid catalysts.
Experimental
All reagents were commercially available and used without
further purification. Melting points were determined on an
X-4 apparatus. IR spectra were determined on a Thermo
123

P. Liu et al.
146.4, 147.7, 149.0, 155.3, 177.3, 177.5, 178.4, 183.3 ppm;
MS (ESI): m/z = 465 ([M ? 1]?).
Scientific Nicolet is 50 spectrometer using KBr disks.
NMR spectra were recorded at room temperature on a
Bruker DRX-500 spectrometer at 500 MHz (1H), 125 MHz
(13C) using DMSO-d6 as the solvent with TMS as internal
standard. Mass spectra were operated at a 3200 Qtrap
instrument with an ESI source.
13-(3-Phenoxyphenyl)-5H-dibenzo[b,i]xanthene-
5,7,12,14(13H)-tetraone (3h, C33H18O6)
ꢀ
Red solid; IR (KBr): m = 3451, 2979, 1637, 1482, 1285,
1
1153, 1093, 1047, 742, 659 cm-1; H NMR (DMSO-d6,
500 MHz): d = 6.69 (d, J = 6.5 Hz, 2H), 6.81 (s, 1H),
6.91 (d, J = 8.0 Hz, 3H), 7.00 (t, J = 7.0 Hz, 1H), 7.17 (t,
J = 8.0 Hz, 1H), 7.26 (t, J = 8.0 Hz, 2H), 7.66 (t,
J = 7.5 Hz, 2H), 7.75 (t, J = 7.0 Hz, 2H), 7.87 (d,
J = 7.5 Hz, 2H), 7.95 (d, J = 7.5 Hz, 2H) ppm; 13C
NMR (DMSO-d6, 125 MHz): d = 32.9, 115.0, 117.5,
117.8, 122.1, 122.7, 125.0, 125.6, 129.0, 129.6, 130.8,
131.7, 133.1, 133.6, 143.8, 155.8, 156.7, 183.4 ppm; MS
(ESI): m/z = 511 ([M ? 1]?).
DES preparation
Choline chloride (100 mmol) and 100 mmol itaconic acid
were mixed in a 250 cm3 round-bottomed flask. The mix-
ture was heated at 80 °C until a clear liquid appeared. It
can be directly used without any further purification.
Typical procedure for preparation of 13-aryl-5H-
dibenzo[b,i]xanthene-5,7,12,14(13H)-tetraones
13-[4-(tert-Butyl)phenyl]-5H-dibenzo[b,i]xanthene-
5,7,12,14(13H)-tetraone (3i, C31H22O5)
ꢀ
A dry 50 cm3 flask was charged with aldehyde (1 mmol),
2-hydroxy-1,4-naphthoquinone (2 mmol), and 1.0 g DES
and the reaction mixture was stirred at 80 °C. The progress
of the reaction was monitored by TLC. After completion of
the reaction, the mixture was cooled to room temperature
and water was added to the reaction mixture. The solid
product was isolated by filtration, washed with water, and
purified by recrystallization from ethanol.
Orange solid; IR (KBr): m = 3420, 2963, 2867, 1681, 1664,
1
1592, 1456, 1358, 1091, 1049, 720, 665 cm-1; H NMR
(DMSO-d6, 500 MHz): d = 1.19 (s, 9H), 5.10 (s, 1H), 7.28
(d, J = 9.5 Hz, 2H), 7.36 (d, J = 9.0 Hz, 2H), 7.73 (s,
1H), 7.87–7.90 (m, 2H), 7.94–7.97 (m, 2H), 8.01 (d,
J = 7.5 Hz, 1H), 8.11–8.13 (m, 2H) ppm; 13C NMR
(DMSO-d6, 125 MHz): d = 31.5, 32.9, 34.6, 115.9, 123.9,
124.6, 124.9, 126.2, 126.5, 126.7, 127.0, 129.2, 130.9,
131.2, 131.4, 131.6, 132.2, 132.3, 134.9, 135.2, 138.9,
149.2, 149.9, 155.6, 177.2, 177.4, 178.3, 183.2 ppm; MS
(ESI): m/z = 475 ([M ? 1]?).
Except for compounds 3c, 3f, 3h–3j, 3q, 3t–3x, all
products are known compounds. The physical and spec-
troscopic data for all known compounds were found to be
identical to those described in the literature.
13-(2-Fluorophenyl)-5H-dibenzo[b,i]xanthene-
13-(2-Hydroxyphenyl)-5H-dibenzo[b,i]xanthene-
5,7,12,14(13H)-tetraone (3j, C27H13FO5)
5,7,12,14(13H)-tetraone (3c, C27H14O6)
ꢀ
ꢀ
Red powder; IR (KBr): m = 3447, 2971, 1640, 1485, 1371,
1279, 1224, 1151, 1050, 744, 730 cm-1; 1H NMR (DMSO-
d6, 500 MHz): d = 6.72 (s, 1H), 7.02–6.94 (m, 2H),
7.16–7.12 (m, 1H), 7.24 (t, J = 7.5 Hz, 1H), 7.67 (t,
J = 7.5 Hz, 2H), 7.75 (t, J = 7.5 Hz, 2H), 7.88 (d,
J = 7.5 Hz, 2H), 7.95 (d, J = 7.5 Hz, 2H) ppm; 13C
NMR (DMSO-d6, 125 MHz): d = 28.7, 114.7 (d,
Brown powder; IR (KBr): m = 3454, 3053, 1646, 1594,
1
1575, 1487, 1355, 1243, 1042, 778, 747 cm-1; H NMR
(DMSO-d6, 500 MHz): d = 5.76 (s, 1H), 7.09–7.15 (m,
2H), 7.22–7.28 (m, 2H), 7.75 (t, J = 7.5 Hz, 1H), 7.83 (t,
J = 4.5 Hz, 3H), 7.88–7.93 (m, 3H), 7.97–8.07 (m, 2H)
ppm; 13C NMR (DMSO-d6, 125 MHz): d = 116.3, 125.3,
125.5, 125.6, 125.8, 128.3, 128.6, 129.9, 130.2, 131.1,
131.6, 133.0, 133.7, 134.5, 134.6, 148.7, 151.2, 177.8,
182.8 ppm; MS (ESI): m/z = 435 ([M ? 1]?).
2JCF = 22 Hz), 122.3 (d, JCF = 224.2 Hz), 125.0, 125.6,
1
3
126.9 (d, JCF = 8.1 Hz), 128.6, 128.7, 130.7 (d,
4JCF = 3.8 Hz), 130.8, 131.9, 133.0, 133.7, 159.4, 161.3,
164.3, 181.9, 183.5 ppm; MS (ESI): m/z = 437
([M ? 1]?).
13-(4-Hydroxy-3-methoxyphenyl)-5H-dibenzo[b,i]xan-
thene-5,7,12,14(13H)-tetraone (3f, C28H16O7)
ꢀ
Dark red solid; IR (KBr): m = 3480, 2972, 1661, 1607,
13-(2-Nitrophenyl)-5H-dibenzo[b,i]xanthene-
1514, 1452, 1275, 1192, 1152, 769, 722 cm-1; H NMR
1
5,7,12,14(13H)-tetraone (3q, C27H13NO7)
ꢀ
(DMSO-d6, 500 MHz): d = 3.64 (s, 3H), 3.74 (s, 1H), 5.96
(s, 1H), 6.58 (s, 2H), 6.79 (s, 1H), 7.77 (dd, J = 1.0 Hz,
7.0 Hz, 2H), 7.80–7.83 (m, 2H), 7.94 (t, J = 7.0 Hz, 2H),
7.98 (dd, J = 1.0 Hz, 7.0 Hz, 2H) ppm; 13C NMR
(DMSO-d6, 125 MHz): d = 32.9, 56.2, 113.9, 115.7,
116.0, 121.9, 123.9, 124.6, 126.5, 126.6, 129.2, 130.0,
130.8, 131.2, 131.7, 132.1, 132.8, 134.8, 135.2, 135.7,
Yellow solid; IR (KBr): m = 3449, 2983, 1659, 1637, 1556,
1438, 1326, 1265, 1090, 1043, 792, 745 cm-1; H NMR
1
(DMSO-d6, 500 MHz): d = 6.18 (s, 1H), 7.42–7.46 (m,
1H), 7.53–7.56 (m, 1H), 7.68 (dd, J = 1.5 Hz, 8 Hz, 2H),
7.67–7.69 (m, 1H), 7.89–7.90 (m, 1H), 7.913–7.93 (m,
2H), 7.98–7.99 (m, 1H), 8.00–8.04 (m, 2H), 8.12–8.15 (m,
1H) ppm; 13C NMR (DMSO-d6, 125 MHz): d = 33.5,
123

Choline chloride and itaconic acid-based deep eutectic solvent as an efficient and reusable…
120.7, 121.9, 122.6, 125.7, 126.3, 129.8, 131.5, 132.5,
134.4, 135.6, 144.7, 148.3, 165.2, 182.8, 183.9 ppm; MS
(ESI): m/z = 464 ([M ? 1]?).
13,13’-(1,4-Phenylene)bis(5H-dibenzo[b,i]xanthene-
5,7,12,14(13H)-tetraone) (3x, C48H22O10)
ꢀ
Dark red solid; m.p.: 323–326 °C; IR (KBr): m = 3446,
2973, 1661, 1607, 1515, 1456, 1276, 1193, 1153, 769, 722,
13-(3-Bromo-5-chloro-2-hydroxyphenyl)-5H-
dibenzo[b,i]xanthene-5,7,12,14(13H)-tetraone
(3t, C27H14BrClO6)
1
625 cm-1; H NMR (DMSO-d6, 500 MHz): d = 5.10 (d,
J = 6.0 Hz, 1H), 5.22 (s, 1H), 7.03 (d, J = 8.5 Hz, 1H),
7.24 (d, J = 8.5 Hz, 1H), 7.34 (t, J = 6.5 Hz, 1H),
7.68–7.77 (m, 8H), 7.81 (d, J = 8.5 Hz, 1H), 7.88–7.92
(m, 8H), 7.95 (t, J = 4.0 Hz, 2H), 7.99 (d, J = 8.5 Hz,
1H), 8.14 (t, J = 6.5 Hz, 2H) ppm; 13C NMR (DMSO-d6,
125 MHz): d = 34.1, 115.0, 122.8, 124.8, 126.5, 126.7,
129.2, 129.7, 130.6, 130.7, 131.0, 131.2, 131.6, 132.3,
134.9, 135.2, 135.5, 135.6, 149.6, 155.7, 177.1, 177.4,
178.1, 183.2 ppm; MS (ESI): m/z = 759 ([M ? 1]?).
ꢀ
Yellow solid; IR (KBr): m = 3445, 2996, 2842, 1657, 1637,
1
1580, 1486, 1282, 1255, 1092, 845, 725 cm-1; H NMR
(DMSO-d6, 500 MHz): d = 5.74 (s, 1H), 7.12 (s, 1H), 7.69
(d, J = 7.5 Hz, 1H), 7.73 (t, J = 8.5 Hz, 2H), 7.86–7.88
(m, 2H), 7.89–7.90 (m, 2H), 7.91 (d, J = 9.0 Hz, 2H), 8.05
(t, 1H) ppm; 13C NMR (DMSO-d6, 125 MHz): d = 28.8,
111.4, 122.5, 126.5, 128.2, 129.5, 130.7, 131.6, 132.5,
134.6, 135.2, 145.5, 147.4, 151.1, 151.2, 177.7, 182.5,
183.1 ppm; MS (ESI): m/z = 546 ([M ? 1]?).
Acknowledgments This work was supported by the Nature Science
Foundation of Hebei Province (No. B2015205182) and the National
Natural Science Foundation of China (No. 21272053).
13-(Thiophen-2-yl)-5H-dibenzo[b,i]xanthene-
5,7,12,14(13H)-tetraone (3u, C25H12O5S)
ꢀ
Dark green solid; IR (KBr): m = 3420, 2973, 1684, 1663,
1
1576, 1355, 1290, 1049, 1008, 757, 714 cm-1; H NMR
References
(DMSO-d6, 500 MHz): d = 5.40 (s, 1H), 6.86–6.88 (m,
1H) 7.08 (d, J = 3.0 Hz, 1H), 7.37 (dd, J = 1.0 Hz,
5.0 Hz, 1H), 7.75 (t, J = 7.0 Hz, 1H), 7.91–7.93 (m, 2H),
7.95–7.98 (m, 1H), 8.03–8.06 (m, 2H), 8.09 (d,
J = 7.0 Hz, 1H), 8.13–8.15 (m, 1H) ppm; 13C NMR
(DMSO-d6, 125 MHz): d = 27.6, 115.3, 123.1, 124.7,
126.4, 126.5, 126.7, 127.3, 129.3, 129.7, 130.9, 131.2,
131.5, 132.3, 135.0, 135.3, 135.7, 144.2, 149.2, 155.8,
177.3, 178.1, 183.0 ppm; MS (ESI): m/z = 425
([M ? 1]?).
1. Singh H, Nand B, Sindhu J, Khurana JM, Sharma C, Aneja KR
(2014) J Braz Chem Soc 25:1178
2. Spatafora C, Barresi V, Bhusainahalli VM, Micco SD, Musso N,
Riccio R, Bifulco G, Condorelli D, Tringali C (2014) Org Biomol
Chem 12:2686
3. Evangelinou O, Hatzidimitriou AG, Velali E, Pantazaki AA,
Voulgarakis N, Aslanidis P (2014) Polyhedron 72:122
4. Ilangovan A, Anandhan K, Prasad K, Vijayakumar P, Ren-
ganathan R, Ananth D, Sivasudha T (2015) Med Chem Res
24:344
5. Singh H, Sindhu J, Khurana JM (2015) Opt Mater 42:449
6. Katori A, Azuma E, Ishimura H, Kuramochi K, Tsubaki K (2015)
J Org Chem 80:4603
7. Jhonsi MA, Srinivasan V, Kathiravan A (2014) Synth Met
196:131
8. Belov VN, Mitronova GY, Bossi ML, Boyarskiy VP, Hebisch E,
Geisler C, Kolmakov K, Wurm CA, Willig KI, Hell SW (2014)
Chem Eur J 20:13162
9. Khaligh NG (2012) Cat Sci Technol 2:2211
10. Tisseh ZN, Azimi SC, Mirzaei P, Bazgir A (2008) Dyes Pigm
79:273
11. Bazgir A, Tisseh ZN, Mirzaei P (2008) Tetrahedron Lett 49:5165
12. Shaterian HR, Rigi F (2015) Res Chem Intermed 41:721
13. Shaterian HR, Azizi K, Fahimi N (2014) Res Chem Intermed
40:1403
13-(Naphthalen-1-yl)-5H-dibenzo[b,i]xanthene-
5,7,12,14(13H)-tetraone (3v, C31H16O5)
ꢀ
Orange solid; IR (KBr): m = 3445, 2976, 1675, 1661, 1590,
1352, 1286, 1192, 1048, 942, 777 cm-1; 1H NMR (DMSO-
d6, 500 MHz): d = 6.31 (s, 1H), 7.46 (t, J = 7.0 Hz, 1H),
7.73 (t, J = 7.5 Hz, 2H), 7.84–7.88 (m, 4H), 7.94–7.97 (m,
5H), 8.08–8.10 (m, 1H), 8.23 (d, J = 8.5 Hz, 2H) ppm; 13
C
NMR (DMSO-d6, 125 MHz): d = 32.5, 123.4, 124.8,
125.3, 125.5, 125.6, 125.7, 126.3, 126.4, 126.6, 129.0,
131.9, 132.5, 133.6, 134.2, 134.4, 137.8, 183.9 ppm; MS
(ESI): m/z = 469 ([M ? 1]?).
14. Khaligh NG, Shirini F (2015) Ultrason Sonochem 22:397
15. Rahmati A (2010) Chin Chem Lett 2:761
16. Li YL, Du BX, Xu XP, Shi DQ, Ji SJ (2009) Chin J Chem
27:1563
17. Shaterian HR, Ranjbar M, Azizi K (2011) J Mol Liq 162:95
18. Shaterian HR, Sedghipour M, Mollashahi E (2014) Res Chem
Intermed 40:1345
19. Shaterian HR, Azizi K (2015) Res Chem Intermed 41:409
20. Khurana JM, Lumb A, Chaudhary A, Nand B (2014) J Heterocycl
Chem 51:1747
21. Liu P, Hao JW, Mo LP, Zhang ZH (2015) RSC Adv 5:48675
22. Tang BK, Row KH (2013) Monatsh Chem 144:1427
4-(5,7,12,14-Tetraoxo-7,12,13,14-tetrahydro-5H-
dibenzo[b,i]xanthen-13-yl)benzaldehyde (3w, C28H14O6)
ꢀ
Dark red solid; IR (KBr): m = 3445, 2976, 1681, 1607,
1577, 1487, 1229, 1195, 1152, 773, 718, 646 cm-1; H
1
NMR (DMSO-d6, 500 MHz): d = 5.21 (s, 1H), 7.71–7.76
(m, 4H), 7.81 (d, J = 8.5 Hz, 2H), 7.88–7.91 (m, 4H),
8.11–8.14 (m, 2H), 9.93 (s, 1H) ppm; 13C NMR (DMSO-
d6, 125 MHz): d = 34.1, 115.0, 122.8, 124.8, 126.5, 129.2,
129.9, 130.6, 131.0, 131.2, 131.6, 132.3, 134.9, 135.2,
135.5, 135.6, 148.4, 149.6, 155.7, 177.1, 177.4, 178.1,
183.2 ppm; MS (ESI): m/z = 447 ([M ? 1]?).
´ ˆ
23. Zhang QH, De Oliveira Vigier K, Royer S, Jerome F (2012)
Chem Soc Rev 41:7108
123

P. Liu et al.
24. del Monte F, Carriazo D, Serrano MC, Gutierrez MC, Ferrer ML
(2014) ChemSusChem 7:999
25. Paiva A, Craveiro R, Aroso I, Martins M, Reis RL, Duarte ARC
(2014) ACS Sustain Chem Eng 2:1063
36. Rajawat A, Khandelwal S, Kumar M (2014) RSC Adv 4:5105
37. Wang P, Ma FP, Zhang ZH (2014) J Mol Liq 198:259
38. Kumar A, Shukla RD, Yadav D, Gupta LP (2015) RSC Adv
5:52062
26. Zhang ZH, Zhang XN, Mo LP, Li YX, Ma FP (2012) Green
Chem 14:1502
39. Liu YH, Deng J, Gao JW, Zhang ZH (2012) Adv Synth Catal
354:441
27. Li PH, Ma FP, Wang P, Zhang ZH (2013) Chin J Chem 31:757
28. Aziizi N, Manochehri Z, Nahayi A, Torkashvand S (2014) J Mol
Liq 196:153
29. Lu J, Li XT, Ma EQ, Mo LP, Zhang ZH (2014) ChemCatChem
6:2854
40. Li PH, Li BL, An ZM, Mo LP, Cui ZS, Zhang ZH (2013) Adv
Synth Catal 355:2952
41. Ma FP, Li PH, Li BL, Mo LP, Liu N, Kang HJ, Liu YN, Zhang
ZH (2013) Appl Catal A Gen 457:34
42. Wang HJ, Zhang XN, Zhang ZH (2010) Monatsh Chem 141:425
43. Guo RY, An ZM, Mo LP, Wang RZ, Liu HX, Wang SX, Zhang
ZH (2013) ACS Comb Sci 15:557
30. Hu HC, Liu YH, Li BL, Cui ZS, Zhang ZH (2015) RSC Adv
5:7720
31. Ma FP, Cheng GT, He ZG, Zhang ZH (2012) Aust J Chem
65:409
44. Li BL, Li PH, Fang XN, Li CX, Sun JL, Mo LP, Zhang ZH
(2013) Tetrahedron 69:7011
32. Azizi N, Dezfooli S, Khajeh M, Hashemi MM (2013) J Mol Liq
186:76
33. Azizi N, Dezfooli S, Hashemi MM (2014) J Mol Liq 194:62
34. Azizi N, Edrisi M (2015) Monatsh Chem. doi:10.1007/s00706-
015-1447-2
45. Zhang P, Zhang ZH (2009) Monatsh Chem 140:199
46. Francisco M, van den Bruinhorst A, Kroon MC (2012) Green
Chem 14:2153
47. Liu YH, Tao XY, Lei LQ, Zhang ZH (2009) Synth Commun
39:580
35. Rokade SM, Garande AM, Ahmad NAA, Bhate PM (2015) RSC
Adv 5:2281
123