Environmentally benign and one-pot synthesis of 14-aryl-14H-dibenzo[a,j] xanthenes catalyzed by acyclic Br?nsted acidic ionic liquid [H-NMP][HSO4] under green conditions

Article abstract of DOI:10.1016/j.crci.2013.08.003

A convenient and efficient direct protocol for the preparation of 14-aryl-14H-dibenzo[a,j]-xanthenes was described. The condensation of 2-naphthol with various aromatic aldehydes in the presence of a catalytic amount of [H-NMP][HSO₄] as a Br?ns

Full text of DOI:10.1016/j.crci.2013.08.003

C. R. Chimie 17 (2014) 41–48
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Full paper/Memoire
Environmentally benign and one-pot synthesis of 14-aryl-
14H-dibenzo[a,j]xanthenes catalyzed by acyclic Brønsted
acidic ionic liquid [H-NMP][HSO4] under green conditions
*
Hossein Naeimi , Zahra Sadat Nazifi
Department of Organic Chemistry, Faculty of Chemistry, University of Kashan, Kashan 87317, Iran
A R T I C L E I N F O
A B S T R A C T
Article history:
A convenient and efficient direct protocol for the preparation of 14-aryl-14H-dibenzo[a,j]-
xanthenes was described. The condensation of 2-naphthol with various aromatic
aldehydes in the presence of a catalytic amount of [H-NMP][HSO4] as a Brønsted acidic
ionic liquid under solvent-free conditions at 110 8C was described. This method has the
following advantages: the reaction workup is very easy, and the catalyst is smoothly
recycled to catalyze the preparation of 14-aryl-14H-dibenzo[a,j]xanthenes with high
yields through a green and one-pot procedure. The corresponding products have been
obtained in excellent yields, with high purity, and in short reaction times.
Received 29 November 2012
Accepted after revision 6 August 2013
Available online 5 October 2013
Keywords:
2-Naphthol
Aldehydes
One-pot reaction
Brønsted Acidic Ionic Liquids
Eco-friendly
ß 2013 Acade´mie des sciences. Published by Elsevier Masson SAS. All rights reserved.
Xanthene
1. Introduction
1,3-dicarbonyl compounds [13]. The most common
synthesis routes to xanthenes included the reaction of
Xanthene derivatives posses a broad range of useful
pharmacological activities such as antibacterial [1], anti-
inflammatory [2], antiviral properties [3]. Furthermore,
these heterocyclic compounds are used for photodynamic
therapy [4]; such compounds are also utilized as antago-
nists of the paralyzing action of zoxazolamine. Some other
compounds find applications in industries such as those of
dyes [5], laser technology [6], and pH-sensitive fluorescent
materials for visualization of biomolecules [7]. These
compounds have been synthesized by many procedures.
Some of the important method included trapping of
benzynes by phenol [8], intermolecular phenyl carbonyl
coupling reactions of aldehydes and 2-naphthol [9],
cyclodehydrations [10], carbon monoxide [11], reaction
of 2-naphthol with formamide for the synthesis of
14H-dibenzo-[a,j]xanthenes [12], aldehydes and cyclic
14H-dibenzo[a,j]xanthene by condensation of 2-naphthol
and aldehydes in the presence of p-toluenesulfonic acid
[14,15], molecular iodine [16], K5CoW12O40Á3H2O/silica–
gel/MW [17], LiBr/MW [18], amberlyst-15 [19],
a-iodoa-
cetates from alkenes/ammonium acetate/I2 [20], cation-
exchange resins [21] as catalysts, Beckmann rearrange-
ment products [22], isonitriles [23], silica sulfuric acid [24],
sulfamic acid [25].
Recently, the use of acidic ionic liquids (ILs) has
achieved considerable importance in organic synthesis,
because of their application as eco-friendly solvents. The
benefits of these compounds are low vapor pressure, non-
inflammability, wide liquid range, reusability, high ther-
mal stability, acidic catalytic activity, and the fact they can
be used instead of conventional organic solvents [26–29].
The synthesis of heterocycles under solvent-free condi-
tions has attracted much attention in synthetic organic
chemistry. However, the above-mentioned methods for
the synthesis of heterocyclic compounds suffer drawbacks
such as long reaction times, low yield, expensive reagents,
*
Corresponding author.
E-mail address: naeimi@kashanu.ac.ir (H. Naeimi).
1631-0748/$ – see front matter ß 2013 Acade´mie des sciences. Published by Elsevier Masson SAS. All rights reserved.
http://dx.doi.org/10.1016/j.crci.2013.08.003

42
H. Naeimi, Z.S. Nazifi / C. R. Chimie 17 (2014) 41–48
Table 1
harsh reaction conditions, toxic organic solvents, and
excess of catalysts.
Synthesis of 14-(4-chloro-3-nitrophenyl)14H-dibenzo[a,j]xanthene with
different amounts of catalyst.
In this research, we wish to report an efficient and green
procedure for the synthesis of 14-aryl-14H-dibenzo[a,j]-
xanthenes. Herein, we describe a new and very convenient
protocol for the condensation of aromatic aldehydes with
2-naphthol to the corresponding 14-aryl-14H-diben-
zo[a,j]xanthanes in the presence of Brønsted acidic ionic
liquid [H-NMP][HSO4] as a homogeneous catalyst under
solvent-free conditions. The catalyst could be recovered
and recycled several times without significant loss of
activity, and with high purity.
Entry
Catalyst loading (mol%)
Time (min)
Yielda (%)
1
2
3
4
5
6
–
120
25
20
8
0
30
65
95
95
95
2
5
10
15
20
7
7
a
Isolated yield.
Table 2
The synthesis of 14-(4-Chloro-3-nitrophenyl)14H-dibenzo[a,j] xanthene
under different temperaturesa.
2. Results and discussion
Entry
Temperature
Yieldb (%)
Initially, in order to optimize the reaction conditions,
we considered the reaction of 2-naphthol and 4-chloro-3-
nitrobenzaldehyde in 2:1 ratio as a model substrate, in the
presence of various catalytic amounts of [H-NMP][HSO4]
as a homogeneous catalyst under solvent-free conditions
at 110 8C (Scheme 1).
1
2
3
4
5
6
50
70
20
50
70
80
95
95
90
100
110
120
The obtained results allowing us to determine the
optimum amount of catalyst are presented in Table 1. In
this reaction, the best results were obtained using 10 mol%
of catalyst (as can be seen from Table 1, entry 4), while a
higher amount of catalyst did not affect reaction times and
yields (Table 1, entry 6).
a
The reaction was carried out in the presence of 10 mol% of ionic liquid
as a catalyst.
b
Isolated yield.
Table 3
Synthesis of 14-(4-nitrophenyl)-14H-dibenzo[a,j] xanthene with diffe-
After optimization of the amount of catalyst, we studied
the reaction of 2-naphthol, 4-chloro-3-nitrobenzaldehyde
as a simple model by using an optimum amount of [H-
NMP][HSO4] at different temperatures under solvent-free
conditions (Table 2). It was found that the best result was
obtained when the reaction was carried out at 110 8C in the
presence of 10 mol% of ionic liquid (Table 2, entry 5).
The efficiency of [H-NMP][HSO4] catalyst in comparison
with that of various catalysts, including some ionic liquids,
was also examined (Table 3). [H-NMP][HSO4] was found to
be the most efficient of all the catalysts tested, in terms of
reaction time, yield, and temperature (Table 3, entry 1 in
compare with entries 2–7 for other catalysts and entries 8–
10 for other ionic liquids).
rent catalysts.
Entry Catalyst
Time Yield Temperature Ref
(min) (%)
(8C)
1
2
3
4
5
6
7
8
9
10
[H-NMP][HSO4]
10
120
180
180
40
96
90
96
98
98
85
97
97
98
90
110
110
r.t
–
Cellulose sulfuric acid
PFPAT
[34]
[1a]
[35]
[32]
[36]
[37]
[38]
[39]
[40]
Boric acid
120
125
90
SiO2–Pr–SO3H
Iodine
150
60
H2SO4/SiO2
125
120
80
[Et3N–SO3H]Cl
[BMIm][BF4]–Mg(BF4)2
[Hmim][HSO4]
25
30
30
125
This can activate the carbon atom of the carbonyl group for
the nucleophilic attack of the position of 2-naphthol. The
After optimization of the reaction conditions, the
reaction of 2-naphthol with several aldehydes was carried
out according to the general experimental procedure
(Scheme 2). The corresponding products are summarized
in Table 4. As can be seen in this Table, the best activity of
aromatic aldehydes was shown with an electron-with-
drawing group (such as –NO2) in para and meta positions.
a
presence of an electron-donating group (such as–OH)
decreased both the reaction rate and the yield of product,
which can be explained by an inactivation of the carbonyl
group via the resonance resulting from the non-bonded
electron pairs of the OH group (Table 4, entry 11).
Scheme 1. Synthesis of 14-(4-chloro-3-nitrophenyl)14H-dibenzo[a,j]xanthene.

H. Naeimi, Z.S. Nazifi / C. R. Chimie 17 (2014) 41–48
43
Table 4
One-pot synthesis of 14-aryl-14H-dibenzo[a,j]xanthenes using a catalytic amount of [H-NMP][HSO4] as a Brønsted acidic ionic liquid under solvent-free
conditions at 110 8C.
Entry
Aldehyde
Product
Time (min)
Yielda
Mp (8C)
Found
Mp (8C) [Ref.]
Reported
1
12
94
183–184
182–183 [31]
CHO
O
2
20
87
212–213
214–215 [31]
Cl
CHO
Cl
O
3
20
96
289–290
287–288 [31]
Cl
Cl
CHO
O
4
17
90
229–230
227–228 [31]
Cl
Cl
Cl
Cl
CHO
Cl
O
5
20
91
250–253
–
Cl
Cl
Cl
CHO
O
6
15
87
213–214
214–215 [31]
NO
2
O N
2
CHO
O
7
10
95
212–213
210–211 [31]
O
N
NO
2
2
CHO
O

44
H. Naeimi, Z.S. Nazifi / C. R. Chimie 17 (2014) 41–48
Table 4 (Continued )
Entry
Aldehyde
Product
Time (min)
10
Yielda
96
Mp (8C)
Found
Mp (8C) [Ref.]
Reported
8
308–309
310–311 [31]
NO
2
O N
2
CHO
O
Cl
9
8
95
232–234
–
O
N
2
NO
2
Cl
CHO
O
10
20
92
240–241
242–243 [32]
HO
OH
CHO
O
11
20
80
138–140
139–140 [33]
OH
HO
CHO
O
12
17
87
197–198
198 [42]
H
C
CH
3
3
CHO
O
13
19
85
172–173
174–176 [41]
OCH
H
CO
3
3
CHO
O
14
17
85
228–230
227–228 [31]
CH
3
H C
3
CHO
O

H. Naeimi, Z.S. Nazifi / C. R. Chimie 17 (2014) 41–48
45
Table 4 (Continued )
Entry
Aldehyde
Product
Time (min)
25
Yielda
82
Mp (8C)
Found
Mp (8C) [Ref.]
Reported
15
204–205
202–203 [31]
OCH
3
H CO
CH
3
O
a
Isolated yield.
Scheme 2. Synthesis of 14-aryl-14H-dibenzo[a,j]-xanthenes.
In this study, 14-aryl-14H-dibenzo[a,j]xanthenes were
prepared using the model reaction of 2-naphthole and
various aromatic aldehydes in the presence of a homo-
geneous catalytic amount of [H-NMP][HSO4] (10 mol %) at
110 8C under solvent-free conditions. After separation
from the product, the catalyst is removable as a by-product
by washing with water, and easily recycled to catalyze the
preparation of 14-aryl-14H-dibenzo[a,j]xanthenes with
excellent yields. The product yields (%) were calculated
as the amount of experimental xanthene (g)/amount of
theoretical xanthene (g) Â 100.
In order to reuse the catalyst after the full separation of
the solid products (3a) from water, the water-containing
Brønsted acidic ionic liquids (BAILs is soluble in water)
were evaporated under vacuum and the catalyst was
recycled several times without any decrease in its catalytic
activity; the yields ranged from 94% to 89% (Fig. 1).
The structures of the products were confirmed by
spectroscopic and physical determinations such as IR, 1H
NMR, 13C NMR, and UV. The infrared spectra of the 14-
(phenyl)14H-dibenzo[a,j]xanthene exhibit
1248 cmÀ1, assigned to (C–O). In the 1H NMR spectra,
the signal around = 6.98–8.41 ppm is assigned to the
protons of the aromatic rings [ (CH = CH)], the signal of the
aliphatic rings
(CH) appears at 6.5 ppm, and in the 13C
NMR spectrum the signal around = 117.34–148.74 ppm is
assigned to the carbons of the aromatic rings (CH = CH),
a band at
n
We also examined the model reaction being conducted
with concentrated sulfuric acid (98% w/w) as a catalyst
under the same conditions to compare ionic liquids with
hazardous H2SO4 (0.5 mmol) under solvent-free conditions
at 110 8C. The reaction was completed in 65 min with 70%
yield. The corrosive properties of sulfuric acid are accen-
tuated by the highly exothermic reactions in which it is
implicated. The danger is greater with concentrated sulfuric
acid and also this is not good from the green chemistry
viewpoint. The catalyst cannot be reused and recycled for
further reactions and is not environmentally safe.
d
n
n
d
and the signal of the aliphatic rings
38.07 ppm.
n(CH) is observed at
2.1. Proposed reaction mechanism
A proposed mechanism for the formation of 14-aryl-
14H-dibenzo[a,j]xanthenes is presented in Scheme 3 [34].
As can be seen, the Brønsted acidic ionic liquid with
hydrogen bonding can activate the carbonyl group of the
aldehyde to decrease the energy of the transition state. Then
2-naphthol attacks the carbonyl group of the activated
aldehyde to afford intermediate (1), and the reaction likely
proceedsviainitialformationofthecarboniumion(2).Then,
the oxonium species (4) is formed in the cyclization reaction
of intermediate (3), which undergoes dehydration to afford
the desired product (5).
3. Conclusions
In this new method, we have described the synthesis of
Fig. 1. Reusability of the catalyst.
14-aryl-14H-dibenzo[a,j]xanthenes using 2-naphthol with

46
H. Naeimi, Z.S. Nazifi / C. R. Chimie 17 (2014) 41–48
Scheme 3. The proposed reaction mechanism.
different kinds of aromatic aldehydes. The use of [H-
NMP][HSO4] as a highly efficient, inexpensive, non-toxic,
easy-workup, and reusable catalyst makes the present
procedure eco-friendly and economically acceptable.
Furthermore, its low cost, its thermal conditions, the fact
that the catalyst is easy to recycle, the short reaction times
needed make this solvent-free method relevant from the
green chemistry viewpoint.
Ltd in high purity. The used solvents were purified by
standard procedures.
4.2. Apparatus
IR spectra were obtained as KBr pellets on a Perkin
Elmer 781 spectrophotometer and on a Nicolet Impact 400
FTIR spectrophotometer. 1H NMR and 13C NMR were
recorded in CDCl3 as the solvent on a Bruker DRX-400
spectrometer with tetramethylsilane as an internal refe-
rence. UV–vis spectra obtained with a PerkinElmer 550
were recorded in CDCl3 solvents. Melting points, obtained
with a Yanagimoto micro melting point apparatus, are
uncorrected. The purity determination of the substrates
and reaction monitoring were accomplished by TLC on
silica-gel polygram SILG/UV 254 plates (Merck).
4. Experimental
4.1. Materials
All commercially available reagents were used without
further purification and purchased from Merck Chemicals

H. Naeimi, Z.S. Nazifi / C. R. Chimie 17 (2014) 41–48
47
4.3. General procedure for the synthesis of [H-NMP][HSO4]
127.95, 127.88, 126.94, 124.45, 123.49, 118.12, 118.01,
34.65; UV (CH2Cl2)/lmax (nm): 246, 230.
1-Methyl-2-pyrolidone (0.2 mol) was charged into a
250-mL three-necked flask containing a magnetic stirrer.
Then an equimolar amount of concentrated sulfuric acid
(98 wt %) was added dropwise slowly into the flask at 80 8C
for 12 h. The mixture was washed by ether three times to
remove non-ionic residues and dried under vacuum by a
rotary evaporator to obtain the viscous clear [H-
NMP][HSO4] compound [30]. The pH of the resulted ionic
liquid (10% w/v) was determined and the obtained pH was
equal to 1.2.
14-(2-Nitrophenyl)14H-dibenzo[a,j]xanthene
yellow solid, mp 213–214 8C (mp 214–215 8C) [31], IR
(KBr)/
(cmÀ1): 3057, 1625, 1593, 1500, 1397, 1346, 1305,
817, 750; 1H NMR (CDCl3, 400 MHz)/
ppm: 7.08 (t, 1H,
J = 8.0, CH), 7.23–7.27 (t, 1H, J = 7.2, Ar), 7.42–7.46 (t, 2H,
J = 7.2, Ar), 7.42–7.49 (m, 3H, Ar), 7.57–7.63 (m, 3H, Ar),
7.81–7.84 (m, 4H, Ar), 8.53–8.55 (d, 2H, J = 8.4, Ar); 13C
(3d):
n
d
NMR/(CDCl3, 100 MHz)/d ppm: 149.4, 147.03, 140.87,
134.14, 132.26, 131.72, 130.97, 129.47, 128.73, 127.59,
127.41, 124,92, 124,67, 122.58, 118.03, 117.58; UV
(CH2Cl2)/lmax (nm): 244, 230.
4.4. A typical procedure for the synthesis of 14-aryl-14H-
dibenzo[a,j]xanthenes
14-(3-Nitrophenyl)14H-dibenzo[a,j]xanthene (3e): yel-
low solid, mp 212–213 8C (mp 210–211 8C) [31], IR (KBr)/
n
(cmÀ1): 3075, 1592, 1527, 1500, 1397, 1346, 1252, 1080,
A mixture of aldehyde (1 mmol, 0.15 g), 2-naphthol
(2 mmol, 0.288 g), [H-NMP][HSO4] (10 mol %, 0.19 g) was
left under solvent-free conditions at 110 8C for the
appropriate time indicated in Table 2. The progress of
the reactions was monitored by TLC (ethyl acetate/
petroleum ether 3:7). After completion of the reaction,
the reaction mixture was cooled, and the mixture was
extracted with (2 Â 10 ml of CH2Cl2) and [H-NMP][HSO4]
was removed as a by-product by washing with water. The
extract was dried on CaCl2 and evaporated to give the
crude product, which was then purified by recrystalliza-
tion from ethanol. Products were characterized by
comparison of their physical and spectral data with those
of authentic samples [31,32].
958, 812, 748; 1H NMR (CDCl3, 400 MHz)/
d ppm: 6.62 (s,
1H, CH), 7.28–7.32 (t, 1H, J = 7.6, Ar), 7.43–7.47 (t, 2H,
J = 7.6, Ar), 7.51–7.53 (d, 2H, J = 8.8, Ar), 7.60–7.64 (t, 2H,
J = 7.2, Ar), 7.81–7.87 (m, 6H, Ar), 8.30–8.32 (d, 2H, J = 8.4,
Ar), 8.42 (s, 1H, Ar); 13C NMR/(CDCl3, 100 MHz)/
d ppm:
148.77, 148.21, 146.94, 134.27, 131.04, 129.57, 129.49,
129.07, 127.25, 124.59, 122.71, 122.04, 121.69, 118.13,
115.87, 37.71; UV (CH2Cl2)/lmax (nm): 246, 228.
14-(4-Nitrophenyl)14H-dibenzo[a,j]xanthene (3f): pale
yellow solid, mp 308–309 8C (mp 310–311 8C) [31], IR
(KBr)/
NMR (CDCl3, 400 MHz)/
n
(cmÀ1): 3068, 1593, 1515, 1341, 1243, 824, 745; 1H
d
ppm: 6.61 (s, 1H, CH), 7.43–7.47
(t, 2H, Ar), 7.50–7.53 (d, 2H, Ar), 7.59–7.63 (t, 2H, Ar), 7.68–
7.70 (d, 2H, Ar), 7.84–7.89 (t, 4H, Ar), 8.00–8.02 (d, 2H, Ar),
8.28–8.30 (d, 2H, Ar); 13C NMR/(CDCl3, 100 MHz)/
d ppm:
152.01, 148.77, 146.29, 131,06, 129.6, 129.07, 128.97,
127.19, 124.59, 123.87, 122.04, 118.07, 115.76, 37.87; UV
(CH2Cl2)/lmax (nm): 248, 228.
14-(Phenyl)14H-dibenzo[a,j]xanthene (3a): pale yel-
low solid, mp 183–184 8C (mp 182–183 8C) [31], IR (KBr)/
n
(cmÀ1): 3061, 1624, 1592, 1513, 1458, 1410, 1248, 1078,
962, 805, 744; 1H NMR (CDCl3, 400 MHz)/
d ppm: 6.50 (s,
1H, CH), 6.98–7.01 (t, 1H, J = 7.6, Ar), 7.13–7.17 (t, 2H,
J = 7.6, Ar), 7.40–7.43 (t, 2H, J = 7.6, Ar), 7.48–7.54 (m, 4H,
Ar), 7.56–7.60 (t, 2H, J = 7.2, Ar), 7.81–7.92 (d, 2H, J = 8.8,
Ar), 7.82–7.84 (d, 2H, J = 8.0, Ar), 8.39–8.41 (d, 2H, J = 8.8,
14-(4-Chloro-3-nitrophenyl)14H-dibenzo[a,j]xanthene
(3 g): yellow solid, mp 232–234 8C, IR (KBr)/
1623, 1592, 1530, 1462, 1350, 1246, 952, 812, 742; 1H
NMR (CDCl3, 400 MHz)/ ppm: 7.27 (s, 1H, CH), 7.29–7.31
n
(cmÀ1): 3054,
d
Ar); 13C NMR/(CDCl3, 100 MHz)/
d
ppm: 148.74, 145.03,
(d, 1H, J = 8.4, Ar), 7.45–7.52 (m, 4H, Ar), 7.62–7.65 (m, 3H,
Ar), 7.84–7.89 (t, 4H, J = 9.2, Ar), 8.03–8.04 (d, 1H, J = 2.0,
Ar), 8.24–8.26 (d, 2H, J = 8.4, Ar); UV (CH2Cl2)/lmax (nm):
246, 232.
131,48, 131.07, 128.88, 128.82, 128.5, 128.29, 126.81,
126.41, 124.26, 122.72, 118.04, 117.34, 38.07, UV (CH2Cl2)/
lmax (nm): 244, 230.
14-(4-Chlorophenyl)14H-dibenzo[a,j]xanthene (3b):
yellow solid, mp 289–290 8C (mp 287–288 8C) [31], IR
14-(2,4-Dichlorophenyl)-14H-dibenzo[a.j]xanthene
(3 h): pale yellow solid, mp 229–230 8C (mp 227–228 8C)
(KBr)/
n
(cmÀ1): 3067, 1624, 1591, 1514, 1585, 1431, 1243,
[31], IR (KBr)/
1401, 1247, 1103, 1072, 960, 864, 836, 807, 743; 1H NMR
(CDCl3, 400 MHz)/ ppm: 6.77 (s, 1H, CH), 6.90–6.92 (d, 1H,
n
(cmÀ1): 3061, 1622, 1591, 1514, 1464, 1430,
1085, 961, 808, 743; 1H NMR (CDCl3, 400 MHz)/
d
ppm:
6.48 (s, 1H, CH), 7.10–7.12 (d, 2H, J = 8.4, Ar), 7. 41–7.47 (m,
4H, Ar), 7.48–7.50 (d, 2H, J = 8.8, Ar), 7.57–7.61 (t, 2H,
J = 7.6, Ar), 7.80–7.82 (d, 2H, J = 8.8, Ar), 7.84–7.86 (d, 2H,
J = 8.0, Ar), 8.32–8.34 (d, 2H, J = 8.4, Ar); 13C NMR/(CDCl3,
d
Ar), 7.28–7.32 (m, 2H, Ar), 7.43–7.50 (m, 4H, Ar), 7.61–7.65
(t, 2H, J = 7.6, Ar), 7.81–7.85 (t, 4H, J = 9.0, Ar), 8.65–8.67 (d,
2H, J = 8.0, Ar); 13C NMR/(CDCl3, 100 MHz)/
d ppm: 148.9,
100 MHz)/
d
ppm: 148.51, 145.01, 131.39, 131.31, 131.20,
142.25, 132.8, 132,71, 132.6, 130.92, 130.59, 129. 3,
128.78, 128.41, 127.06, 124.57, 123.17, 118.11, 117.46,
34.24; UV (CH2Cl2)/lmax (nm): 248, 230.
130.18, 129.83, 129.19, 128.91, 127.60, 125.14, 123.77,
118.21, 117.50, 39.87; UV (CH2Cl2)/lmax (nm): 244, 230.
14-(2-Chlorophenyl)14H-dibenzo[a,j]xanthene
white solid, mp 212–213 8C (mp 214–215 8C) [31], IR
(KBr)/
(cmÀ1): 3059, 1625, 1592, 1461, 1400, 1243, 1032,
959,808; 1H NMR (CDCl3, 400 MHz)/
ppm: 6.81 (s, 1H,
(3c):
14-(2,3-Dichlorophenyl)-14H-dibenzo[a.j]xanthene
(3i): white solid, mp 250–253 8C, IR (KBr)/
1625, 1593, 1514, 1459, 1405, 1401, 1251, 1107, 1070, 962,
869, 813, 807, 746; 1H NMR (CDCl3, 400 MHz)/
ppm: 6.85
y
(cmÀ1): 3057,
n
d
d
CH), 6.92 (m, 2H, Ar), 7.40–7.44 (m, 3H, Ar), 7.48–7.51 (d,
(s, 1H, CH), 6.87–6.89 (d, 1H, J = 8.0, Ar); 7.09–7.11 (d, 2H,
J = 8.8, Ar), 7.32–7.35 (d, 1H, J = 9.2, Ar), 7.44–7.51 (m, 4H,
Ar), 7.62–7.85 (t, 4H, J = 9.2, Ar), 8.69–8.67 (d, 2H, J = 8.4,
Ar); UV (CH2Cl2)/lmax (nm): 248, 230.
2H, J = 8.8, Ar), 7.61–7.64 (m, 5H, Ar), 8.74–8.76 (d, 2H,
J = 8.4, Ar); 13C NMR/(CDCl3, 100 MHz)/
d
ppm: 148.95,
143.59, 131.83, 130.91, 130.15, 129.61, 129.06, 128.67,

48
H. Naeimi, Z.S. Nazifi / C. R. Chimie 17 (2014) 41–48
14-(3-Hydroxyphenyl)-14H-dibenzo[a,j]xanthene (3j):
Pale Pink solid, mp 172–173 8C (mp 174–176 8C) [32]; IR
(KBr)/
(cmÀ1): 3068,1593, 1513, 1401, 1251, 1242, 810;
1H NMR (CDCl3, 400 MHz)/
ppm: 3.58 (s, 3 H), 6.42 (s, 1
H), 6.47 (d, 1H, J = 8.2), 7.05 (t, 2H, J = 8.4), 7.13 (d, J = 7.5 Hz,
1 H), 7.39 (t, 2H, J = 7.2), 7.43 (d, 2H, J = 9.0), 7.53 (t, 2H,
J = 7.6), 7.72–7.82 (m, 4H), 8.36 (d, 2H, J = 8.7).
Appendix A. Supplementary data
n
Supplementary data associated with this article can be
found, in the online version, at http://www.sciencedirect.-
com and http://dx.doi.org/10.1016/j.crci.2013.08.003.
d
References
14-(4-Hydroxyphenyl)-14H-dibenzo[a,j]xanthene
(3k): Pink solid, mp 137–138 8C (mp 138–140 8C) [33]; IR
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(KBr)/
1H NMR (CDCl3, 400 MHz)/
6.43(s, 1H, CH), 6.55–8.36 (m, 16H, Ar-H); 13C NMR/(CDCl3,
100 MHz)/ ppm: 37.41, 115.70, 118.00, 118.39, 123.10,
n
(cmÀ1): 3404,1592, 1511, 1401, 1250, 1242, 816;
d
ppm:4.97 (br s, 1H, OH),
d
124.62, 127.23, 129.11, 129.20, 129.78, 131.53, 131.81,
137.90, 149.11, 154.24.
14-(3-Methoxy)14H-dibenzo[a,j]xanthene (3l): Pale
pink solid, mp 173–174 8C (mp 174–176 8C) [40]; IR
(KBr)/
1247, 1050, 964, 806, 743; 1H NMR (CDCl3, 400 MHz)/
ppm: 3.63 (s, 3H, OCH3), 6.45 (s, 1H, CH), 6.51 (dd, 2H,
n
(cmÀ1): 3067, 3014, 2932, 1582, 1454, 1431, 1400,
d
J = 7.5, ArH), 7.02–7.46 (m, 6H, ArH), 7.55 (t, 2H, J = 7.5, ArH),
7.78 (t, 4H, J = 7.5, ArH), 8.39 (d, 2H, J = 7.5 Hz, ArH).
14-(4-Methoxy)14H-dibenzo[a,j]xanthene (3 m): pink
solid, mp 204–205 8C (mp 202–203 8C) [31], IR (KBr)/
n
(cmÀ1): 3062, 1594, 1509, 1458, 1398, 1247, 960, 814,
744; 1H NMR (CDCl3, 400 MHz)/
d ppm: 6.45 (s, 1H, CH),
6.67–6.69 (d, 2H, J = 8.4, Ar), 7.40–7.44 (m, 4H, Ar), 7.47–
7.49 (d, 2H, J = 8.8, Ar), 7.56–7.60 (t, 2H, J = 7.2, Ar), 7.78–
7.80 (d, 2H, J = 8.8, Ar), 7.82–8.84 (d, 2H, J = 8.0, Ar), 8.38–
8.40 (d, 2H, J = 8.4, Ar); 13C NMR/(CDCl3, 100)/
d ppm: 37.14,
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126.40, 126.79, 128.77, 128.84, 129.20, 131.11, 131.45,
137.42, 148.68, 157.86; UV (CH2Cl2)/lmax (nm): 246, 230.
14-(3-Methyl)14H-dibenzo[a,j]xanthene (3n): White
solid, mp 196–197 8C (mp 197–198 8C) [41], IR (KBr)/
n
(cmÀ1): 3018, 2922, 1623, 1591, 1513, 1457, 1401, 1249,
961, 806, 806, 743; 1H NMR (CDCl3, 400 MHz)/
d ppm: 2.14
(s, 3H, CH3), 6.42 (s, 1H, CH), 6.76 (d, 1H, J = 7.5, ArH), 7.03
(t, 1H, J = 7.5 Hz, ArH), 7.20–7.41 (m, 4H, ArH), 7.43 (d, 2H,
J = 8.75, ArH), 7.54 (t, 2H, J = 7.5, ArH), 7.75 (t, 4H, J = 10,
ArH), 8.35 (d, 2H, J = 7.5, ArH).
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14-(4-Methyl)14H-dibenzo[a,j]xanthene (3o): pale yel-
low solid, mp 228–230 8C (mp 227–228 8C) [31], IR (KBr)/
n
(cmÀ1): 3069, 1623, 1591, 1531, 1458, 1399, 1244, 961,
810, 741; 1H NMR (CDCl3, 400 MHz)/
d ppm: 6.46 (s, 1H,
CH), 6.95–6.97 (d, 2H, J = 8.0, Ar), 7.39–7.43 (m, 4H, Ar),
7.47–7.50 (d, 2H, J = 9.2, Ar), 7.56–7.60 (t, 2H, J = 9.2, Ar),
7.78–7.80 (d, 2H, J = 8.8, Ar), 7.82–8.84 (d, 2H, J = 8.0, Ar),
8.39–8.41 (d, 2H, J = 8.8, Ar); 13C NMR/(CDCl3, 100)/
d ppm:
20.91, 37.64, 117.46, 118.02, 122.72, 124.22, 126.77,
128.11, 128.77, 128.79, 129.19, 131.08, 131.46, 135.91,
142.14, 148.68; UV (CH2Cl2)/lmax (nm): 247, 232.
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Acknowledgement
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The authors are grateful to University of Kashan for
supporting this work by Grant No. 159148/9.