Proceedings of the 4th International Conference on Nanostructures (ICNS4)

12-14 March, 2012, Kish Island, I.R. Iran

Sulfonic Acid Functionalized Single-Walled Carbon Nanotubes: A Highly Efficient and

Reusable Catalyst for Green Synthesis of 14-Aryl-14H-dibenzo[a,j]xanthene Derivatives
under Solvent-free Conditions
R. Fareghi Alamdari*; M. Golestanzadeh; F. Agend; N. Zekri
Department of Chemistry and Chemical Engineering, Malek-Ashtar University of Technology, Tehran, 16765-3454,
Iran
*reza_fareghi@yahoo.com

Abstract: In the present work, high density of sulfonated carbon nanotubes were prepared by reacting concentrated

sulphuric acid with single-walled carbon nanotubes at high temperature and characterized by Scanning Electron
Microscopy (SEM), Transmission Electron Microscopy (TEM), Fourier Transform Infrared (FT-IR), Raman
spectroscopy and Neutralization titration. The heterogeneous catalyst, which is a strong protonic solid acid, was used
for efficient and environment synthesis of 14-aryl-14H-dibenzo[a,j]xanthene derivatives. The obtained results showed
that this catalyst is a robust heterogeneous catalyst for the synthesis of 14-aryl-14H-dibenzo[a,j]xanthenes and can be
recovered by simple filtration and reused without loss of its activity. In addition, excellent yields, solvent free
conditions, easy work-up and non-toxicity of the catalyst are the other noteworthy advantages of the present method.

Keywords: Heterogeneous catalyst; Functionalization; Characterization; Dibenzoxanthene; Solvent-free

Introduction
Xanthene and dibenzoxanthene derivatives are important
heterocyclic compounds because of their wide range of
therapeutic and pharmacological properties such as
antibacterial, antiviral, anti-inflammatory activities [1].
These compounds are also used as dyes, as
luminescentory sensors, in laser technologies, in
fluorescent materials for the visualization of biomolecules
and in photodynamic therapy [2]. Recently, numerous
methods have been developed for the synthesis of
dibenzoxanthenes. The synthesis of 14-aryl-14Hdibenzoxanthene has been reported by the condensation
of 2-naphtol and aldehydes in the presence of ptoluenesulfonic acid [3], sulfamic acid [4], ZrO(OTf)2 [5]
and so on. However several of these methodologies
involve harsh conditions or longer reaction time, leaving
considerable scope for development of further clean,
facile and efficient process for the synthesis of these
important molecules.
Recently the use of carbon nanotubes as catalyst has
attracted much attention in the context of green
chemistry. In order to optimize the use of carbon
nanotubes in various applications, such as catalyst
supports in heterogeneous catalysis it is necessary to
attach functional groups on the surface of carbon
nanotubes, because the physical and chemical properties
of carbon nanotubes can be dramatically influenced by
surface modification with organic and inorganic species,
which makes them useful for various application,
particularly as solid acid catalyst [6].
In this letter, we would like to report a new, efficient and
suitable method for the synthesis of 14-aryl-14Hdibenzo[a,j]xanthenes by use of sulfonic acid
functionalized carbon nanotubes.

Scheme1- Synthesis of dibenzoxanthenes by use of

sulfonated carbon nanotubes.

Experimental
Melting points were measured on a digital melting point
IA 8103 apparatus. All chemical reagents used in our
experiments were of analytical grade and were used as
received without further purification. All reactions were
monitored by TLC and all yields refer to isolated
products. 1H-NMR spectra were recorded on a BrukerAvance 500 MHz instrument using tetramethylsilane
(TMS) as internal standard. Fourier transform spectra
(FT-IR) recorded on a Nicolet 860 instrument. SEM
images were taken on a Philips XL30 SEM. TEM images
were recorded with a JEOL JEM-2010 microscope
operated with an acceleration voltage of 200 kV. The
Raman spectra were recorded with an Almega Thermo
Nicolet Dispersive Raman Spectrometer- second
harmonic@532 nm. SWCNTs used in this work were
purchased from Research Institute of Petroleum Industry.
Sulfonated single-walled carbon nanotubes provided by
reported work [7]. The SWCNTs were first sonicated for
30 min and then heated at 80C for 4h in the mixture of
1:1 concentrated HNO3 (65%) and HCl (37%) to remove
catalyst particles. These steps also introduced oxygen
containing groups mainly carboxyl groups on the
SWCNTs. The pure SWCNTs were filtered and washed
for times, then dried at 120C overnight. Then 50 ml
concentrated H2SO4 (98%) and 100 mg pure SWCNTs
were mixed in a dry flask and then sonicated for 30 min,

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Proceedings of the 4th International Conference on Nanostructures (ICNS4)

12-14 March, 2012, Kish Island, I.R. Iran

followed by heating to 300C in an electrothermal heater

under dinitrogen atmosphere for 18h. After the treatment
the suspension was diluted by water and filtered. The
solids were washed to remove excess acid and dried at
120C to obtain sulfonated SWCNTs. After procedure for
preparation of sulfonated carbon nanotubes, in a round
bottom flask 60 mg sulfonated single-walled carbon
nanotubes was added to mixture of 2-naphtol (4mmol)
and different benzaldehydes (2mmol). The reaction
heated under reflux conditions. The progress of the
reaction was monitored by TLC (EtOAc: n-hexane 5:1).
At the end of the reaction, the mixture was cooled to
room temperature and 15 ml chloroform was added. The
product was recovered from the filtrate by evaporation on
a rotary evaporator. The resulting solid materials were
recrystallized from ethanol to give the pure product.

cm-1 was assigned to C-S stretching mode. The broad line

centered at 3544 cm-1 is the contribution from the OH
groups in sulfonic acid.

Results and Discussion

Fig. 2- FT-IR spectrum of SO3H@SWCNTs.

The sulfonated single-walled carbon nanotubes were

prepared according to the procedure described in above.
The microscopic characterization by SEM and TEM are
shown in Fig. 1. Comparing the single-walled carbon
nanotubes before and after functionalization, this shows
that the SWCNT is covered by a layer of the foreign
matter. The foreign matter is the groups of the sulfonic
acids that are shown as marked by the white arrows.

The covalent functionalization was also demonstrated by

Raman spectroscopy. Fig. 3 shows the Raman spectrum
of SO3H@SWCNTs. The D line of SO3H@SWCNTs
significantly increased, indicating the strong damage to
the side wall of SWCNTs or the formation of fragments
caused by the functionalization.

552
1332
1560

1200

3544

Fig. 3- Raman spectrum of SO3H@SWCNTs.

Fig. 1- TEM (a,b), SEM (c,d) images of SWCNTs before

and after sulfonation.
FT-IR spectroscopy was employed to investigate the
nature of these surface groups. As shown in fig. 2 the FTIR spectrum of SO3H@SWCNTs show a weak line at
1560 cm-1. This line was assigned to the C=C stretching
mode of SWCNT graphic layers. This mode is weak due
to the symmetry of dipole moment. The SO2OH groups
can be identified with the lines at 1332 and 1200 cm-1
representing the SO2 asymmetric and symmetric
stretching modes. In low frequency range the line at 552

1018

In continuation of our interest on the application of

heterogeneous catalysts, we wish to report a simple,
efficient and practical approach for the synthesis of
xanthene derivatives by using SO3H@SWCNTs as ecofriendly catalyst (Scheme 1). SO3H@SWCNT is
environmentally benign and solid acid catalyzed the
condensation of 2-naphtol and wide range of aromatic
aldehydes under solvent-free conditions. As indicated in
Table 1, in all cases the reaction gives the products in
good yields and high selectivity and prevents problems
which may associate with solvent use such as cost,
handling, safety and pollution. In these experiments, the
reaction mixture isolated with chloroform and the
remaining catalyst washed exhaustively with ethanol and

Proceedings of the 4th International Conference on Nanostructures (ICNS4)

12-14 March, 2012, Kish Island, I.R. Iran

deionized water successively, and then reloaded with

fresh reagents for further runs. Apparently, recycling of
the catalyst is possible for five successive times without
significant loss of activity (Table 1, row 2). The identities
of the products were confirmed by Mp, and 1H-NMR and
IR spectral data.
row

Aldehyde

Product

Isolated
yield (%)

Mp C

91

312-314

94

290-291

[2].G. H. Mahdavinia; S. Rostamizadeh; A. M. Amani; Z.

Emdadi; Ultrasono. Chem. 16(2009)7.
[3]. A. R. Khosropour; M. M. Khodaei; H. Moghanian;
Synlett. (2005)955.
[4]. B. Rajitha; B. S. Kumar; Y. T. Reddy; Tetrahedron
letters. 46(2005)8691.
[5]. I. Mohammapoor-Baltork; M. Moghadam; V.
Mirkhani; S. Tangestaninejad; H. R. Tavakoli; Chinese
Chemical letters. 22(2011)9.
[6]. F. Peng; L. Zhang; H. J. Wang; P. Lv; H. Yu; Carbon
43(2005)2405.
[7]. H. Yu; Y. Jin; Z. Li; F. Peng; H. Wang; journal of
solid state chemistry, 181(2008)432.

(94,93,91,91
,89)a

90

182-183

91

200-202

88

226-228

90

258-259

OCH3

a: Isolated yield after recycling catalyst.

Conclusions
In
conclusions,
we
have
demonstrated
that
SO3H@SWCNTs can be used as green and reusable
catalyst for efficient synthesis of 14-aryl-14Hdibenzo[a,j]xanthene derivatives under solvent-free
conditions. In addition, this method offers several
advantages including high yields, easy work up, reusable
catalyst and solvent free conditions.

Acknowledgment
We are grateful to Malek-Ashtar University
Technology for financial support of this work.

of

References
[1]. S. Kantevari; M. V. Chary; A. P. R. Das; S. V. N.
Vupplapati; N. Lingaiah; Catalysis Communicatio,
9(2008)1575.

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