RSC Advances
Page 6 of 8
DOI: 10.1039/C6RA02266A
thus confirming the identity of the HPW and CsPW
catalyst samples used. UV spectra were recorded on a UV-
VIS spectrophotometer Shimadzu UV-2600.
[6] J. Xiong, Y. Huang, H. Zhang and L. Hou, Food Sci.
Technol. Res., 2014, 20, 207–216.
[7] J. Iqbal and R. R. Srivastava, J. Org. Chem., 1992, 57,
The acidic heteropoly salt CsPW was prepared according to
the method described previously33 by adding dropwise the
required amount of the aqueous solution of cesium
carbonate (0.47 M) to the aqueous solution of HPW (0.75
M) with stirring at room temperature. The precipitate
obtained was aged in an aqueous mixture for 48 h at room
temperature and dried in a rotary evaporator at 45 °C/3 kPa
and after that in an oven at 150 °C/0.1 kPa for 1.5 h. CsPW
had a surface area of 111 m2g-1, pore volume of 0.07 cm3g-1,
and pore diameter of 24 Å. The acid strength of CsPW was
characterized calorimetrically using ammonia and pyridine
adsorption; its proton sites were found somewhat weaker
than those in the bulk HPW but stronger than in zeolites.29
2001–2007.
[8] R. Ballini, G. Bosica, S. Carloni, L. Ciaralli, R.
Maggi and G. Sartori, Tetrahedron Lett., 1998, 39,
6049–6052.
[9]P. A. Procopiou, S. P. D. Baugh, S.S. Flack and G. G. A.
Inglis, J. Org. Chem., 1998, 63, 2342–2347
[10] R. Dalpozzo, A. De Nino, L. Maiuolo, A. Procopio,
M. Nardi, G. Bartoli and R. Romeo, Tetrahedron Lett. ,
2003, 44, 5621–5624.
The reactions were carried out in a 10 mL glass reactor
equipped with a magnetic stirrer and a condenser. In a
typical run, a mixture (3.0–5.0 mL) of the substrate (0.75–
10.0 mmol), dodecane or undecane (0.5–1.0 mmol GC
internal standards) and the catalyst (HPW (5 mg, 1.5 µmol)
or CsPW (10–30 mg, 3.0–10.0 µmol), acetic anhydride or
acetic acid and a solvent (if any) was intensely stirred
under air at room temperature. The reactions were followed
by gas chromatography (GC) using a Shimadzu 17
instrument fitted with a Carbowax 20 M capillary column
and a flame ionization detector. After an appropriate
reaction time, the stirring was stopped and after quick
catalyst settling down aliquots were taken and analyzed by
CG. The mass balance and the product selectivity and yield
were determined using dodecane or undecane as internal
standards. Any difference in the mass balance was
attributed to the formation of oligomers, which were
unobservable by GC. The products were identified by GC-
MS by comparison with authentic compounds. Mass
spectra were obtained on a Shimadzu QP2010-PLUS
instrument operating at 70 eV.
[11] J. S. Yadav, A. V. Narsaiah, B. V. S. Reddy, A. K.
Basak and K. Nagaiah, J. Mol. Catal. A, 2005, 230,
107–111.
[12] I. V. Kozhevnikov, Catalysts for Fine Chemicals,
Catalysis by Polyoxometalates, vol. 2, Wiley,
Chichester, 2002.
[13] T. Okuhara, N. Mizuno and M. Misono, Appl. Catal.
A, 2001, 222, 63–77.
[14] E. V. Gusevskaya, ChemCatChem, 2014, 6, 1506–
1515.
[15] G. Sartori and R. Maggi, Chem. Rev., 2006, 106,
1077−1104.
[16] T. Okuhara, M. Kimura, T. Kawai, Z. Xu and T.
Nakato, Catal. Today, 1998, 45, 73–77
[167 T. Okuhara, Chem. Rev., 2002, 102, 3641–3666.
In order to control catalyst leaching and the possibility of a
homogeneous reaction, the CsPW catalyst was removed
from the reaction mixture by centrifugation then a fresh
portion of substrate was added to the supernatant and the
reaction was allowed to proceed.
[18] J. Zhang, X. Liu, M. N. Hedhili, Y. Zhu and Yu Han,
ChemCatChem, 2011, 3, 1294–1298.
[19] V. V. Costa, K. A. da Silva Rocha, I. V. Kozhevnikov,
E. F. Kozhevnikova and E. V. Gusevskaya, Catal. Sci.
Technol., 2013, 3, 244–250.
Acknowledgements
[20] V. V. Costa, K. A. da Silva Rocha, R. A. Mesquita, E.
F. Kozhevnikova, I. V. Kozhevnikov and E. V.
Gusevskaya, ChemCatChem, 2013, 5, 1884–1890.
Financial support and scholarships from CNPq, CAPES,
FAPEMIG, and INCT-Catálise (Brazil) are acknowledged.
[21] A. L. P. de Meireles, M. dos Santos Costa, K. A. da
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