Application of nanosized Cu0.5Co0.5Fe2O4 spinel ferrite as a nanocatalyst in the synthesis of 14-aryl-14H-dibenzo[a,j]xanthene derivatives under solvent-free conditions

Article abstract of DOI:10.1002/jccs.201400148

Copper and cobalt substituted spinel ferrites Cu_1-xCo_xFe₂O₄ (0 ≤ X ≤ 1) have been synthesized by using hydrothermal method. The resultant spinel ferrites were systematically characterized by different techniques

Full text of DOI:10.1002/jccs.201400148

JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Article
Application of Nanosized Cu0.5Co0.5Fe2O4 Spinel Ferrite as a Nanocatalyst in the
Synthesis of 14-Aryl-14H-dibenzo[a,j]xanthene Derivatives under Solvent-free
Conditions
Reza Fareghi-Alamdari,a* Mohsen Golestanzadehb and Negar Zekria
aCollege of Chemistry and Chemical Engineering, Malek-Ashtar University of Technology, Tehran, 16765-3454, I. R.
Iran
bDepartment of Organic Chemistry, Faculty of Chemistry, University of Kashan, Kashan, 87317, I. R. Iran
(Received: Mar. 26, 2014; Accepted: Jun. 25, 2014; Published Online: Sept. 9, 2014; DOI: 10.1002/jccs.201400148)
Copper and cobalt substituted spinel ferrites Cu1-xCoxFe2O4 (0 £ X £ 1) have been synthesized by using
hydrothermal method. The resultant spinel ferrites were systematically characterized by different tech-
niques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray
spectroscopy (EDX), and Fourier transform infrared spectroscopy (FT-IR). It was indicated that all the re-
sultant spinel ferrites obtained by the hydrothermal method had the single-phase crystalline. The resultant
spinel ferrites were employed in the synthesis of 14-aryl-14-H-dibenzo[a,j]xanthene derivatives. It was
found that the nanocatalyst Cu0.5Co0.5Fe2O4 displays the best performance in the synthesis of 14-aryl-14-
H-dibenzo[a,j]xanthenes. The catalyst was reused several times without significant loss of its activity for
the preparation of desired product. In addition, high yields of the products, solvent-free conditions and re-
usability of the catalyst are other worthwhile advantages of the present study.
Keywords: Nanocatalyst; Spinel ferrite; Xanthene; Reusability; Solvent-free.
INTRODUCTION
The synthesis of nanosized spinel ferrites (with the
much attention. Spinel ferrites which have reversed spinel
type structure are found to be highly active toward many
organic reactions.7
general formula MFe2O4 (e.g. M = Mn, Co, Ni, Cu, Zn, Mg)
has become an important part of modern ceramic research.
Recently there have been extensive efforts in the investiga-
tion and evaluation of spinel ferrites (MFe2O4) due to their
special physical and chemical properties.1 The unique
structural, electronic, magnetic and catalytic properties of
nanosized transition metal oxides provide potential appli-
cation in different fields such as MRI contrast agent2 prepa-
ration of high density recording device, gas sensors,3 and
high efficient catalyst.4 Also, spinel ferrites could be di-
rectly synthesized via the hydrothermal method.5 However,
many other synthesis approaches such as co-precipitation,
sol-gel, microemulsion, and hydrothermal have been used
for preparation of spinel ferrite nanoparticles.6 Co-precipi-
tation is highly pH sensitive and is not preferred for com-
plex systems with more than two materials ions.6h In the
microemulsion method, although the crystal growth or par-
ticle agglomeration is controlled effectively, only small
quantities of final desired products could be obtained due
to the constraints of low reagent concentrations required
for this synthetic approach. Nevertheless, among the other
approaches, hydrothermal method has recently received
Over the last decades, xanthene derivatives, espe-
cially 14-aryl-14-H-dibenzo[a,j]xanthene derivatives, have
emerged as an important category of heterocyclic com-
pounds. Among the heterocyclic compounds, xanthenes
are an important class of fused heterocycles with an array
of biological and pharmacological properties such as anti-
viral,8 antibacterial,9 and anti-inflammatory10 activities
(Scheme 1).
Scheme 1 Selected Example of Bio-active Xanthenes
* Corresponding author. Tel: +98(21)22970277; Fax: +98(21)22970195; Email: reza_fareghi@yahoo.com
Supporting information for this article is available on the www under http://dx.doi.org/10.1002/jccs.201400148
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Because of these remarkable properties of xanthenes,
1 1), (4 0 0), (4 2 2), (5 1 1) and (4 4 0) major lattice plane
revealed the cubic spinel phase with Fd3m space group. In
addition, the clear lattice plane of (1 1 1) and (2 2 2) are
present. These results emphasized the presence of only one
spinel phase without any significant impurities. The
CuFe2O4 nanosized spinel ferrite exhibits different patterns
due to cubic spinel phase and a considerable amount of
CuO and Fe2O3 (Figure 1a). Substitution of copper with co-
balt increases the overall crystanillity of the spinel phase.
The XRD pattern of CoFe2O4 (Figure 1c) describes the for-
mation of single phase cubic spinel structure with sharp
peak attributed to (311) reflection indicating that the crys-
tanillites are preferentially oriented along (311) plane. The
breadth of the Bragg peak is a combination of both instru-
ment and sample dependent effects. To decouple these con-
tributions, it is important to collect a diffraction pattern
from the line broadening of a standard material such as sili-
con to determine the instrumental broadening. The cor-
rected instrumentation broadening b corresponding to the
diffraction peak of Cu1-XCoxFe2O4 (x = 0.0, 0.5 and 1.0)
was estimated by using the below relation:
many useful synthetic procedures have been developed for
their preparation. Different catalysts such as Bronsted ac-
ids,11 Lewis acids,12 heteropoly acids,13 and ionic liquids,14
have been developed for the synthesis of dibenzoxan-
thenes. However, in spite of their potential applications,
many published articles have been reported having severe
conditions such as poor yields, use of excessive amount of
catalyst, toxic organic solvent and nonreusable catalysts.
Therefore, in this paper we applied new procedure in the
synthesis of 14-aryl-14-H-dibenzo[a,j]xanthenes using
spinel ferrites Cu1-xCoxFe2O4 (0 £ X £ 1) as nanocatalysts
(Scheme 2).
Cu1-xCoxFe2O4 catalyzed synthesis of 14-
aryl-14-H-dibenzo[a,j]xanthenes
Scheme 2
b = b1 – b2
RESULTS AND DISCUSSION
Characterization of the Cu1-xCoxFe2O4
The crystallite sizes (Dc) of Cu1-xCoxFe2O4 nanopar-
ticles were calculated by using the Debey–Scherrer equa-
tion (see Table S2, supplementary data):
The XRD patterns and the corresponding parameters
of the CuFe2O4, Cu0.5Co0.5F2O4, and CoFe2O4 are shown in
Figure 1 and Table S2. In general, the presence of (2 2 0), (3
Kl
Dc =
bcos q
where b is the breadth of the observed diffraction peak at its
half-intensity maximum, K is the so-called shape factor,
which usually takes a value of about 0.9, and l is the wave-
length of X-ray source used in XRD instrument. XRD dif-
fraction data of Cu1-XCoxFe2O4 for the most intense reflec-
tion are shown in Table S2. As can be seen from these data,
the crystallite sizes of CuFe2O4, Cu0.5Co0.5Fe2O4, and
CoFe2O4 are 18, 22, and 20 nm respectively.
Figure 2 shows the FT-IR spectra of CuFe2O4,
Cu0.5Co0.5Fe2O4, Cu0.25Co0.75Fe2O4, and CoFe2O4 spinel
ferrite nanoparticles. In general, two important broad
bands of metal–oxygen are observed in all of the spinel, es-
pecially spinel ferrites. Generally the highest one, n1, was
observed in the range of 550-600 cm-1, corresponds to in-
trinsic stretching vibrations of the metal at the tetrahedral
site, [Mtetra«O], whereas the lowest band, n2, was ob-
served in the range of 450–385 cm-1, is assigned to octahe-
Fig. 1. XRD patterns of a) CuFe2O4 b) Cu0.5Co0.5Fe2O4
c) CoFe2O4.
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Synthesis of Dibenzoxanthenes by Using Cu0.5Co0.5Fe2O4
dral metal stretching [Mocta«O]. No clear peak attributed
to octahedrally coordinate metal ions has been observed
due to the detection limit of our FT-IR instrument, which is
expected to be less than 400 cm-1. The bands at 2923 cm-1,
and 2845 cm-1 are related to stretching mode of C–H group
and the bands at about 1060-1120 cm-1 attributed to C–O
stretching mode. The broad band centered at 3430 cm-1
could be assigned to O–H stretching mode for arising from
the surface hydroxyl groups on the spinel ferrite nanoparti-
cles. The absorption band at 1630 cm-1 on spectra refers to
the vibration of remainder H2O in the sample.
14-aryl-14H-dibenzo[a,j]xanthene derivatives. Initially,
the reaction parameters such as effect of solvent, tempera-
ture, and catalyst were optimized in the reaction of 2-naph-
thol (1) and 3-nitrobenzaldehyde (2b) in the presence of
Cu1-xCoxFe2O4 spinel ferrites as model reaction (Table 1).
First the reaction of 2-naphthol (1) with 3-nitrobenzalde-
hyde (2b) in the presence of catalytic amount of the
Cu1-xCoxFe2O4 (0.3 g) under solvent-free conditions at 70
°C was performed (Table 1, entries 1-5). We observed that
the Cu0.5Co0.5Fe2O4 was the best catalyst in the model reac-
tion. To choose the solvent and temperature, the model re-
action was tested in different solvents such as n-hexane,
CH3CN, CH3NO2 and also under solvent-free conditions at
room temperature to 100 °C (Table 1, entries 6-13). As this
table shows, entry 8 gave the best result for the medium and
temperature of the reaction. Therefore, solvent-free condi-
tions were chosen as the reaction medium. Also, the opti-
mized temperature of the reaction was chosen at 70 °C.
Also, the model reaction was performed with different
amounts of Cu0.5Co0.5Fe2O4 (Table 1, entries 13-16). The
best result was obtained with 0.3 g of the catalyst. In addi-
tion, we performed the model reaction in the absence of the
catalyst. This reaction was developed 5% only.
The general morphologies of the nanosized spinel
ferrites were investigated by SEM are shown in Figure 3.
SEM images were used to see the grain micro-structure of
the nanoparticles, which would provide a better view of the
grain development and grain sizes. These figures indicate
that the samples were obtained by this method as uniform
in both morphology and crystalline size. From the SEM im-
ages, it is also clear that grains have different morphologies
than spherical. A broad size distribution is observed, which
consists of nearly octahedral crystals with an average size
of about 30 nm. The grain sizes measured of Cu1-xCoxFe2O4
(x = 0, 0.25, 0.50, 0.75 and 1) are 48, 34, 24, 24, and 29 nm,
respectively.
To generalize the optimum conditions, various deriv-
Synthesis of 14-aryl-14H-dibenzo[a,j]xanthenes cata-
lyzed by Cu1-xCoxFe2O4
atives of 14-aryl-14H-dibenzo[a,j]xanthene were prepared
from the one-pot reaction mixture of 2-naphthol (1) and the
appropriate aromatic aldehyde (2a-2o) in the presence of
Cu0.5Co0.5Fe2O4 (0.3 g) under solvent-free conditions. The
time of the reaction, yield, turnover frequency (TOF), and
melting points of the products are summarized in Table 2.
As shown in Table 2, aromatic aldehydes with electron-
withdrawing groups such as NO2, CN, and Cl (Table 2, en-
tries 1-5) accelerate rate of the reaction compared with the
electron-donating groups (Table 2, entries 7-14). In addi-
The prepared catalysts were used for the synthesis of
Fig. 3. SEM images of a) Cu0.5Co0.5Fe2O4 b)
Cu0.25Co0.75Fe2O4 c) Cu0.75Co0.25Fe2O4 d)
CoFe2O4 e) CuFe2O4.
Fig. 2. FT-IR spectra of a) CuFe2O4 b) Cu0.5Co0.5Fe2O4
c) Cu0.25Co0.75Fe2O4 d) CoFe2O4.
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tion, the practical synthetic efficiency of this reaction was
investigated by the reaction of terphtaldehyde (2o) and
2-naphthol (1). We expected that both of the carbonyl
groups on the aromatic ring of aldehyde would react with
2-naphthol (1). But we observed that one of the carbonyl
groups react with (1) and another carbonyl group was
unreacted, because of the steric effects between ortho-hy-
drogens of the benzene and xanthene ring (Table 2, entry
15).
Scheme 3 The proposed mechanism
The proposed reaction mechanism for the
Cu0.5Co0.5Fe2O4 catalyzed synthesis of 14-aryl-14H-diben-
zo[a,j]xanthenes using 2-naphthol and aldehyde is shown
in Scheme 3. First, the aldehyde is first activated by
Cu0.5Co0.5Fe2O4 to give I. Nucleophilic attack of 2-naph-
thol on I affords II which in turn activated by Cu0.5Co0.5Fe2O4
to afford carbocation III. Nucleophilic attack of second
molecule of 2-naphthol to carbocation III, gives the
oxonium species IV and V respectively which is subse-
quently converted to the dibenzoxanthene VI and release
Cu0.5Co0.5Fe2O4 for the next catalytic cycle.
Therefore, the reusability of the catalyst was checked by
separating the Cu0.5Co0.5Fe2O4 from the reaction mixture of
2-naphthol (1) and 4-nitrobenzaldehyde (2a) by simple fil-
The reusability of the Cu0.5Co0.5Fe2O4 is of great im-
portance from synthetic and economical points of view.
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Synthesis of Dibenzoxanthenes by Using Cu0.5Co0.5Fe2O4
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Synthesis of Dibenzoxanthenes by Using Cu0.5Co0.5Fe2O4
tration, washing with ethanol and drying in a vacuum oven
at 70 °C for 7 hours prior to reuse in subsequent reactions.
The recovered catalyst can be reused at least 6 runs in sub-
sequent reactions without significant loss in the product
yield (Figure 4). As shown in Figure 4, the Turnover
frequencie (TOF) of the catalyst was decreased after six
catalytic cycle ( from 4.45 to 2.93 h-1). Because the time of
the reaction was increased and the yield of the product was
also decayed, TOF or turnover rate is the number of passes
through the catalytic cycle per unit time (min or h). This
number is usually determined by taking the number of
moles of the product produced, dividing that by the number
of moles of the catalyst used in the reaction, then dividing
that by the time to produce the given amount of product.
Scientific papers often report mol% of catalyst used. This
refers to the fraction of catalyst used relative to the amount
of limiting reactant present.
was carried out using Carlo ERBA model EA-1108 analyzer.
XRD patterns were obtained by the X-ray diffractometer (Philips
PW-1800). The particle size and external morphology of the fine
calcined powders were characterized by SEM (Philips XL30). All
samples were coated with gold at 10 mA for 2 min. prior to SEM
analysis. The EDX analysis was studied by Philips XL30 micro-
scope.
Preparation of the Cu1-xCoxFe2O4: The Cu1-xCoxFe2O4
nanocatalysts were prepared as described in Scheme 4. First, the
hexadecyltrimethylammonium bromide (CTAB) (1 g) was dis-
solved in 35 mL of distilled water. Then, (1 g) FeCl3.6H2O was
added to it and was stirred for 10 min (S1). Then, the appropriate
amounts of CuCl2.2H2O and CoCl2.6H2O salts (see Table S1, sup-
plementary data) were dissolved in distilled water (S2). The S2
was added by a burette into the S1 (S3). Then an aqueous solution
of NaOH was introduced dropwise into the S3 solution (pH =
10-11, black precipate). The mixture was stirred for 0.5 h. The re-
sultant product was transformed to an autoclave. The autoclave
was kept at 160 °C for 72 h. After three days, the autoclave was al-
lowed to cool down to room temperature. The desired
Cu1-xCoxFe2O4 (0 £ X £ 1) was washed several times with distilled
water and dried at room temperature.
EXPERIMENTAL
Materials and apparatus: The chemicals were purchased
from Aldrich and Merck companies. Melting points were deter-
mined by using IA-8103 apparatus. IR spectra were recorded with
KBr pellets in the range of 400-4000 cm-1 with FT-IR Nicolet-860
spectrometer. 1H NMR spectra were recorded in CDCl3 solvent on
a Brucker-Avance 500 MHz spectrometer using tetramethylsilane
(TMS) as an internal standard. The thermal analysis (C, H, and N)
Synthetic route for the preparation of the
catalysts
Scheme 4
General procedure for the synthesis of 14-aryl-14H-di-
benzo[a,j]xanthenes in the presence of Cu0.5Co0.5Fe2O4 under
solvent-free conditions: In a 25 mL flask equipped with a con-
denser and magnetic stirring bar, a mixture of 2-naphthol (4
mmol), aromatic aldehyde (2 mmol), and Cu0.5Co0.5Fe2O4 (0.9
mmol, 0.3 g) was heated at 70 °C under solvent-free conditions
for the appropriate time. The progress of the reaction was moni-
tored by TLC (EtOAc: n-hexane). After completion of the reac-
tion, the mixture was cooled to room temperature and 25 mL
CHCl3 was added. The catalyst was filtered by simple filteration.
Fig. 4. Reusability of the Cu0.5Co0.5Fe2O4.
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The obtained liquid was heated by evaporation on a rotary evapo-
rator. The remained solid material was recrystallized from etha-
nol to afford the pure product. All of the desired products were
identified by FT-IR, 1H NMR and melting points.
Compound 3e): mp = 213-215 °C, IR (KBr) (n cm-1): 3057,
1
1622, 1591, 1400, 1243, 1030, 960, 808. H-NMR (500 MHz,
CDCl3), d (ppm): 6.84 (1H, s, CH), 6.92-6.98 (2H, m, Ar-H),
7.28-7.30 (1H, m, Ar-H), 7.41-7.48 (3H, m, Ar-H), 7.51-7.53
(2H, d, 3J = 8 Hz, Ar-H) 7.64-7.67 (2H, t, 3J = 8 Hz, Ar-H), 7.82-
Reusability of the catalyst
3
7.86 (4H, m, Ar-H), 8.77-8.79 (2H, d, J = 7.9 Hz, Ar-H). Anal.
The reusability of the Cu0.5Co0.5Fe2O4 is of great impor-
tance from synthetic and economical points of view. Therefore,
the reusability of the catalyst was checked by separating the cata-
lyst from the reaction mixture by simple filtration, washing with
ethanol and drying in a vacuum oven at 70 oC for 7 h before being
used with fresh 2-naphtol and aldehyde. The catalyst can be re-
used six times without any loss of its catalytic activity.
Spectroscopic and physical data
Calcd for C27H17ClO: C, 82.54; H, 4.36%. Found: C, 82.62; H,
4.04%. 14-(Phenyl)-14H-dibenzo[a,j]xanthene (Table 2, Com-
pound 3f): mp = 182-184 °C, IR (KBr) (n cm-1): 3069, 3016,
1
1591, 1513, 1398, 1247, 1076, 960, 808, 696. H-NMR (500
MHz, CDCl3), d (ppm): 6.53 (1H, s, CH), 7.01-7.04 (1H, t, 3J =
3
7.8 Hz, Ar-H), 7.17-7.20 (2H, t, J = 7.9 Hz, Ar-H), 7.43-7.46
(2H, t, 3J = 7.8 Hz, Ar-H), 7.52-7.54 (2H, d, 3J = 8.1 Hz, Ar-H),
7.56-7.58 (2H, d, 3J = 8 Hz, Ar-H), 7.60-7.63 (2H, t, 3J = 8.1 Hz,
Ar-H), 7.82-7.84 (2H, d, 3J = 7.9 Hz, Ar-H), 7.85-7.87 (2H, d, 3J
= 8 Hz, Ar-H), 7.43-7.45 (2H, d, 3J = 8 Hz, Ar-H). Anal. Calcd for
C27H18O: C, 90.47; H, 5.06%. Found: C, 90.55; H, 4.94%.
14-(3-Methylphenyl)-14H-dibenzo[a,j]xanthene (Table 2,
Compound 3g): mp = 197-199 °C, IR (KBr) (n cm-1): 3047,
3016, 1619, 1587, 1515, 1249, 809. 1H-NMR (500 MHz, CDCl3),
d (ppm): 2.18 (3H, s, CH3), 6.46 (1H, s, CH), 6.80–6.82 (2H, d, 3J
= 8 Hz, Ar-H), 7.05–7.08 (2H, d, 3J = 8.1 Hz, Ar-H), 7.40–7.61
(6H, m, Ar-H), 7.79–7.84 (4H, m, Ar-H), 8.40–8.42 (2H, d, 3J = 8
Hz, Ar-H). Anal. Calcd for C28H20O: C, 90.29; H, 5.41%. Found:
C, 90.35; H, 5.35%. 14-(4-Methylphenyl)-14H-dibenzo[a,j]-
xanthene (Table 2, Compound 3h): mp = 226-228 °C, IR (KBr)
(n cm-1): 3070, 3019, 1591, 1511, 1399, 1245, 962, 811, 741.
1H-NMR (500 MHz, CDCl3), d (ppm): 2.16 (3H, s, CH3), 6.49
(1H, s, CH), 6.97-6.99 (2H, d, 3J = 8 Hz, Ar-H), 7.42-7.45 (4H, m,
Ar-H), 7.50-7.52 (2H, d, 3J = 7.8 Hz, Ar-H), 7.59-7.62 (2H, t, 3J =
8 Hz, Ar-H), 7.80-7.82 (2H, d, 3J = 7.8 Hz, Ar-H), 7.84-7.86 (2H,
d, 3J = 8 Hz, Ar-H), 8.42-8.44 (2H, d, 3J = 7.8 Hz, Ar-H). Anal.
Calcd for C28H20O: C, 90.29; H, 5.41%. Found: C, 90.25; H,
5.15%. 14-(4-Isopropylphenyl)-14H-dibenzo[a,j]xanthene
(Table 2, Compound 3i): mp = 240-242 °C, IR (KBr) (n cm-1):
3048, 1621, 1578, 1510, 1244, 806. 1H-NMR (500 MHz, CDCl3),
d (ppm): 2.22 (6H, d, 2CH3), 3.1 (1H, m, CH), 6.46(1H, s, CH),
14-(4-Nitrophenyl)-14H-dibenzo[a,j]xanthene (Table 2,
Compound 3a): mp = 312-313 °C, IR (KBr) (n cm-1): 3070,
1
1621, 1589, 1513, 1340, 1239, 961, 806. H-NMR (500 MHz,
3
CDCl3), d (ppm): 6.63 (1H, s, CH), 7.46-7.49 (2H, t, J = 8 Hz,
Ar-H), 7.53-7.55 (2H, d, 3J = 7.8 Hz, Ar-H), 7.62-7.65 (2H, t, 3J =
8Hz, Ar-H), 7.70-7.71 (2H, d, 3J = 7.8 Hz, Ar-H), 7.86-7.89 (4H,
m, Ar-H), 8.02-8.03 (2H, d, 3J = 8 Hz, Ar-H), 8.30-8.32 (2H, d, 3J
= 7.8 Hz, Ar-H). Anal. Calcd for C27H17NO3: C, 80.38; H, 4.25;
N, 3.47%. Found: C, 80.40; H, 4.33; N, 3.41%. 14-(3-Nitrophen-
yl)-14H-dibenzo[a,j]xanthene (Table 2, Compound 3b): mp =
214-216°C, IR (KBr) (n cm-1): 3066, 1590, 1519, 1397, 1352,
1238, 1079, 958, 804, 745. 1H-NMR (500 MHz, CDCl3), d (ppm):
6.64 (1H, s, CH), 7.30-7.34 (1H, t, 3J = 7.9 Hz, Ar-H), 7.46-7.49
3
(2H, t, J = 8 Hz, Ar-H), 7.54-7.56 (2H, d, J = 8 Hz, Ar-H),
3
3
7.63-7.66 (2H, t, J = 7.9 Hz, Ar-H), 7.83-7.89 (6H, m, Ar-H),
3
8.33-8.35 (2H, d, J = 8 Hz, Ar-H), 8.45 (1H, s, Ar-H). Anal.
Calcd for C27H17NO3: C, 80.38; H, 4.25; N, 3.47%. Found: C,
80.45; H, 4.30; N, 3.37%. 14-(4-Cyanophenyl)-14H-dibenzo-
[a,j]xanthene (Table 2, Compound 3c): mp = 338-340 °C, IR
(KBr) (n cm-1): 3026, 2221, 1635, 1591, 1558, 1500, 1449, 1374,
1245, 1169, 960, 810. 1H-NMR (500 MHz, CDCl3), d (ppm): 6.54
(1H, s, CH), 7.12-7.15 (4H, m, Ar-H), 7.30-7.33 (4H, m, Ar-H),
3
7.55-7.58 (2H, m, Ar-H), 7.84-7.87 (4H, t, J = 8.2 Hz, Ar-H),
8.27-8.30 (2H, t, 3J = 8.2 Hz, Ar-H). Anal. Calcd for C28H17NO:
C, 87.71; H, 4.47; N, 3.65%. Found: C, 87.55; H, 4.65; N, 3.64%.
14-(4-Chlorophenyl)-14H-dibenzo[a,j]xanthene (Table 2,
Compound 3d): mp = 290-292 °C, IR (KBr) (n cm-1): 3068,
3
6.84–6.86 (2H, d, J = 8 Hz, Ar-H), 7.12–7.41 (4H, m, Ar-H),
7.48–7.53 (4H, m, Ar-H), 7.68–7.71 (4H, m, Ar-H), 7.86–7.88
(2H, d, 3J = 8 Hz, Ar-H). Anal. Calcd for C30H24O: C, 89.97; H,
6.04%. Found: C, 90.25; H, 5.85%. 14-(3-Hydroxyphenyl)-
14H-dibenzo[a,j]xanthene (Table 2, Compound 3j): mp =
263-265 °C, IR (KBr) (n cm-1): 3451, 3056, 1593, 1512, 1237,
813, 697. 1H-NMR (500 MHz, CDCl3), d (ppm): 4.55 (1H, s, OH),
6.47-6.50 (2H, m, CH, Ar-H), 6.91 (1H, s, Ar-H), 7.04-7.07 (1H,
t, 3J = 8.1 Hz, Ar-H), 7.21-7.23 (1H, d, 3J = 8 Hz, Ar-H),
7.43-7.47 (2H, t, 3J = 7.8 Hz, Ar-H), 7.50-7.52 (2H, d, 3J = 8 Hz,
1
3026, 1620, 1591, 1484, 1242, 1082, 961, 807. H-NMR (500
MHz, CDCl3), d (ppm): 6.50 (1H, s, CH), 7.13-7.15 (2H, d, 3J = 8
Hz, Ar-H), 7.44-7.52 (6H, m, Ar-H), 7.60-7.63 (2H, t, 3J = 7.9 Hz,
Ar-H), 7.83-7.84 (2H, d, 3J = 7.9 Hz, Ar-H), 7.86-7.88 (2H, d, 3J
= 8 Hz, Ar-H), 8.34-8.36 (2H, d, 3J = 7.8 Hz, Ar-H). Anal. Calcd
for C27H17ClO: C, 82.54; H, 4.36%. Found: C, 82.59; H, 4.44%.
14-(2-Chlorophenyl)-14H-dibenzo[a,j]xanthene (Table 2,
1348
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© 2014 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim J. Chin. Chem. Soc. 2014, 61, 1341-1350

JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Synthesis of Dibenzoxanthenes by Using Cu0.5Co0.5Fe2O4
3
(2H, d, J = 8 Hz, Ar-H), 9.79 (1H, s, CHO). Anal. Calcd for
Ar-H), 7.61-7.63 (2H, t, 3J = 8.1 Hz, Ar-H), 7.79-7.81 (2H, d, 3J =
3
7.8 Hz, Ar-H), 7.85-7.87 (2H, d, J = 8.1 Hz, Ar-H), 8.40-8.42
C28H18O2: C, 87.02; H, 4.69%. Found: C, 87.15; H, 4.65%.
(2H, d, 3J = 8 Hz, Ar-H). Anal. Calcd for C27H18O2: C, 86.61; H,
4.85%. Found: C, 87.01; H, 4.84%. 14-(4-Methoxyphenyl)-
14H-dibenzo[a,j]xanthene (Table 2, Compound 3k): mp =
204-205 °C, IR (KBr) (n cm-1): 3042, 1625, 1594, 1512, 1251,
ACKNOWLEDGEMENTS
We gratefully acknowledge the financial support by
Malek-Ashtar University of Technology (MUT).
1
1236, 811. H-NMR (500 MHz, CDCl3), d (ppm): 3.62 (3H, s,
3
OCH3), 6.45 (1H, s, CH), 6.67–6.69 (2H, d, J = 7.9 Hz, Ar-H),
REFERENCES
7.27–7.40 (4H, m, Ar-H), 7.42–7.44 (4H, m, Ar-H), 7.78–7.80
1. Polshettiwar, V.; Luque, R.; Fihri, A.; Zhu, H.; Bouhrara,
M.; Basset, J.-M. Chem. Rev. 2011, 111, 3036-3075.
2. Barcena, C.; Sra, A. K.; Chaubey, G. S.; Khemtong, C.; Liu,
J. P.; Gao, J. Chem. Comm. 2008, 2224-2226.
3
3
(2H, d, J = 8 Hz, Ar-H), 8.02–8.04 (2H, d, J = 8 Hz, Ar-H),
8.38–8.40 (2H, d, 3J = 7.9 Hz, Ar-H). Anal. Calcd for C28H20O2:
C, 86.57; H, 5.19%. Found: C, 87.22; H, 4.79%. 14-(2-Methoxy-
phenyl)-14H-dibenzo[a,j]xanthene (Table 2, Compound 3l):
mp = 258-260 °C, IR (KBr) (n cm-1): 3055, 3023, 1592, 1404,
1242, 1156, 1100, 960, 807, 744. 1H-NMR (500 MHz, CDCl3), d
(ppm): 4.30 (3H, s, OCH3), 6.65-6.68 (1H, t, 3J = 7.8 Hz, Ar-H),
3. Mukherjee, K.; Majumder, S. B. Sens. Actuators, B 2012,
162, 229-236.
4. a) Ashiq, M. N.; Naz, F.; Malana, M. A.; Gohar, R. S.; Ahmad,
Z. Mater. Res. Bull. 2012, 47, 683-686; b) Mangrulkar, P. A.;
Joshi, M. M.; Tijare, S. N.; Polshettiwar, V.; Labhsetwar, N.
K.; Rayalu, S. S. Int. J. Hydrogen Energ. 2012, 37, 10462-
10466.
3
6.89-6.91 (1H, d, J = 8 Hz, Ar-H), 6.99 (1H, s, CH), 7.00-7.04
3
3
(1H, t, J = 7.8 Hz, Ar-H), 7.22-7.23 (1H, d, J = 8 Hz, Ar-H),
7.40-7.43 (2H, t, 3J = 8.1 Hz, Ar-H), 7.49-7.51 (2H, d, 3J = 8 Hz,
5. a) Mostafa, N. Y.; Hessien, M. M.; Shaltout, A. A. J. Alloy
Compd. 2012, 529, 29-33; b) Huo, J.; Wei, M. Mater. Lett.
2009, 63, 1183-1184.
3
Ar-H), 7.55-7.58 (2H, t, J = 8.1 Hz, Ar-H), 7.78-7.84 (4H, m,
3
Ar-H), 8.60-8.62 (2H, d, J = 7.9 Hz, Ar-H). Anal. Calcd for
6. a) Kim, Y. I.; Kim, D.; Lee, C. S. Physica B 2003, 337, 42-51;
b) Liu, X. M.; Fu, S. Y.; Huang, C. J. Mater. Sci. Eng. B 2005,
121, 255-260; c) Hutlova, A.; Niznansky, D.; Rehspringer, J.
L.; Estournès, C.; Kurmoo, M. Adv. Mater. 2003, 15, 1622-
1625; d) Moumen, N.; Pileni, M. P. Chem. Mater. 1996, 8,
1128-1134; e) Liu, X.-M.; Yang, G.; Fu, S.-Y. Mater. Sci.
Eng. C 2007, 27, 750-755; f) Baykal, A.; Kasapo—lu, N.;
Köseo—lu, Y.; Toprak, M. S.; Bayrakdar, H. J. Alloy Compd.
2008, 464, 514-518; g) Liu, Q.; Sun, J.; Long, H.; Sun, S.;
Zhong, X.; Xu, Z. Mater. Chem. Phys. 2008, 108, 269-273;
h) Chen, Q.; Rondinone, A. J.; Chakoumakos, B. C.; Zhang,
J. Z. J. Magn. Magn. Mater. 1999, 194, 1-7.
C28H20O2: C, 86.57; H, 5.19%. Found: C, 86.95; H, 5.55%.
14-(2-Hydroxy-4-methoxyphenyl)-14H-dibenzo[a,j]xanthene
(Table 2, Compound 3m): mp = 210-211 °C, IR (KBr) (n cm-1):
3398, 3156, 3057, 1594, 1508, 1462, 1399, 1228, 1102, 1010,
1
812, 746. H-NMR (500 MHz, CDCl3), d (ppm): 4.30 (3H, s,
OCH3), 5.90 (1H, s, OH), 6.65-6.68 (1H, m, Ar-H), 6.89-6.91
(1H, m, Ar-H), 7.14 (1H, s, CH), 7.00-7.04 (1H, m, Ar-H),
7.22-7.23 (1H, m, Ar-H), 7.40-7.43 (2H, m, Ar-H), 7.49-7.51
(2H, m, Ar-H), 7.55-7.58 (2H, m, Ar-H), 7.78-7.84 (4H, m, Ar-
H), 8.60-8.62 (1H, m, Ar-H). Anal. Calcd for C28H20O3: C, 83.15;
H, 4.98%. Found: C, 83.65; H, 4.15%. 14-(5-Bromo-2-hydroxy-
phenyl)-14H-dibenzo[a,j]xanthene (Table 2, Compound 3n):
mp = 219-221 °C, IR (KBr) (n cm-1): 3535, 3431, 3057, 1603,
1460, 1405, 1253, 1189, 1120, 812. 1H-NMR (500 MHz, CDCl3),
d (ppm): 5.98 (1H, s, OH), 6.65-6.99 (2H, m, Ar-H), 6.89-6.93
(1H, m, Ar-H), 7.20 (1H, s, CH), 7.22-7.24 (1H, m, Ar-H), 7.26-
7.28 (1H, m, Ar-H), 7.40-7.43 (2H, m, Ar-H), 7.49-7.51 (2H, m,
Ar-H), 7.55-7.58 (2H, m, Ar-H), 7.78-7.82 (3H, m, Ar-H),
8.60-8.62 (1H, m, Ar-H). Anal. Calcd for C27H17BrO2: C, 71.54;
H, 3.78%. Found: C, 70.98; H, 4.11%. 14-(4-Formylphenyl)-
14H-dibenzo[a,j]xanthene (Table 2, Compound 3o): mp =
310-311 °C, IR (KBr) (n cm-1): 3060, 2923, 2852, 2765, 1691,
7. a) Velinov, N.; Koleva, K.; Tsoncheva, T.; Manova, E.;
Paneva, D.; Tenchev, K.; Kunev, B.; Mitov, I. Catal. Com-
mun. 2013, 32, 41-46; b) Fareghi-Alamdari, R.; Hosseinabadi,
Z.; Khouzani, M. J. Chem. Sci. 2012, 124, 827-834.
8. Lambert, R. W.; Martin, J. A.; Herrett, J. H.; Parkes, K. E. B.;
Thomas, G. J. Chem. Abstr. 1997, 126, p212377y.
9. Hideo, T. Chem. Abstr. 1981, 95, 80922b.
10. Poupelin, J. P.; Saint-Ruf, G.; Foussard-Blanpin, O.;
Narcisse, G.; UchidaErnouf, G.; Lacroix, R. Eur. J. Med.
Chem. 1978, 13, 67-73.
11. a) Fareghi-Alamdari, R.; Golestanzadeh, M.; Agend, F.;
Zekri, N. C. R. Chim. 2013, 16, 878-887; b) Venu Madhav, J.;
Thirupathi Reddy, Y.; Narsimha Reddy, P.; Nikhil Reddy,
M.; Kuarm, S.; Crooks, P. A.; Rajitha, B. J. Mol. Catal.
A:Chem. 2009, 304, 85-87; c) Naik, M. A.; Sachdev, D.;
Dubey, A. Catal. Commun. 2010, 11, 1148-1153; d) Kokare,
N. D.; Sangshetti, J. N.; Shinde, D. B. Chin. Chem. Lett.
2008, 19, 1186-1189; e) Seyyedhamzeh, M.; Mirzaei, P.;
1
1595, 1513, 1243, 819. H-NMR (500 MHz, CDCl3), d (ppm):
6.58 (1H, s, CH), 7.17–7.19 (2H, d, 3J = 8 Hz, Ar-H), 7.42–7.45
(2H, t, 3J = 7.8 Hz, Ar-H), 7.50–7.68 (4H, m, Ar-H), 7.70–7.78
3
(4H, m, Ar-H), 7.82–7.86 (2H, t, J = 7.6 Hz, Ar-H), 8.33–8.35
J. Chin. Chem. Soc. 2014, 61, 1341-1350
© 2014 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.jccs.wiley-vch.de
1349

Article
Fareghi-Alamdari et al.
Bazgir, A. Dyes Pigm. 2008, 76, 836-839; f) Karimi-Jaberi,
Mirjalili, B. B. F.; Bamoniri, A.; Akbari, A. Chin. Chem.
Lett. 2011, 22, 45-48; e) Hong, M.; Cai, C. J. Fluorine Chem.
2009, 130, 989-992.
Z.; Keshavarzi, M. Chin. Chem. Lett. 2010, 21, 547-549; g)
Rajitha, B.; Sunil Kumar, B.; Thirupathi Reddy, Y.;
Narsimha Reddy, R.; Sreenivasulu, N. Tetrahedron Lett.
2005, 46, 8691-8693; h) Mohammadi Ziarani, G.; Badiei, A.
R.; Azizi, M. Sci. Iran. 2011, 18, 453-457; i) Naeimi, H.;
Nazifi, Z. J. Nanopart. Res. 2013, 15, 1-11.
13. a) Amini, M. M.; Seyyedhamzeh, M.; Bazgir, A. Appl.
Catal., A 2007, 323, 242-245; b) Rivera, T. S.; Sosa, A.;
Romanelli, G. P.; Blanco, M. N.; Pizzio, L. R. Appl. Catal., A
2012, 443–444, 207-213.
12. a) Mohammadpoor-Baltork, I.; Moghadam, M.; Mirkhani,
V.; Tangestaninejad, S.; Reza Tavakoli, H. Chin. Chem. Lett.
2011, 22, 9-12; b) Eshghi, H.; Bakavoli, M.; Moradi, H.
Chin. Chem. Lett. 2008, 19, 1423-1426; c) Su, W.; Yang, D.;
Jin, C.; Zhang, B. Tetrahedron Lett. 2008, 49, 3391-3394; d)
14. a) Gong, K.; Fang, D.; Wang, H. L.; Zhou, X. L.; Liu, Z. L.
Dyes Pigm. 2009, 80, 30-33; b) Zolfigol, M. A.; Khakyzadeh,
V.; Moosavi-Zare, A. R.; Zare, A.; Azimi, S. B.; Asgari, Z.;
Hasaninejad, A. C. R. Chim. 2012, 15, 719-736; c) Naeimi,
H.; Nazifi, Z. S. C. R. Chim. 2014, 17, 41-48.
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