Preparation of heteropoly acid/porous hybrid materials and investigation of their catalytic behavior in the synthesis of perimidine

Article abstract of DOI:10.1002/jccs.201000095

Aseries of hybrid heteropoly acids (HPA) were prepared. The HPA/NaYand HPA/NaY/MCM-41 hybrids of the synthesized catalysts were characterized using XRD, BET, TGA, SEM and FT-IR techniques. The results show that reasonable amount of HPA in HPA/NaY and HPA/

Full text of DOI:10.1002/jccs.201000095

Journal of the Chinese Chemical Society, 2010, 57, 683-689
683
Preparation of Heteropoly Acid/Porous Hybrid Materials and Investigation
of their Catalytic Behavior in the Synthesis of Perimidine
M. Zendehdel,* A. Mobinikhaledi, H. Alikhani and N. Jafari
Chemistry Department, Arak University, Dr. Beheshti Ave, Arak, Iran
A series of hybrid heteropoly acids (HPA) were prepared. The HPA/NaY and HPA/NaY/MCM-41 hy-
brids of the synthesized catalysts were characterized using XRD, BET, TGA, SEM and FT-IR techniques.
The results show that reasonable amount of HPA in HPA/NaY and HPA/NaY/MCM-41 hybrids remains
even after washing with water, which indicates that heteropoly anions were strongly bonded to the porous
materials. The catalytic properties of the hybrid catalysts were examined for the preparation of 2-(4-
nitrophenyl)-2,3-dihydro-1H-perimidine. The yield for perimidine by different catalysts was in order of
HPA/NaY > HPA/NaY/MCM-41 > NaY > HPA > MCM-41.
Keywords: Heteropoly acids; HPA/NaY; HPA/NaY/MCM-41; Perimidine.
INTRODUCTION
Heteropoly acids (HPAs) have proved to be the alter-
result of their biological activities.31-33 The well established
method for the preparation of perimidines involves the di-
rect reaction of 1,8-diaminonaphtalene with a carbonyl
group which may needs extended reaction times, difficult
workup or harsh reaction conditions.34,35 This has led to
several synthetic methods of perimidines by using different
acid catalyst.36-43 However the most of these procedures
mainly focused on the enhancing of the reaction yields, and
rarely attentions has paid to the role of different used inor-
ganic acids as catalyst in the mechanism of reaction. Re-
cently, the use of heterogeneous catalysts, like heteropoly
acids and zeolites44-47 in organic synthesis has attracted
considerable attention. They have many advantages such
as suitable acidity, low cost, thermal stability, nontoxic and
environmentally safe.
native of traditional acid catalysts, such as sulfuric acid and
aluminum chloride, due to their strong acidity and harmless
for environmental. The low surface area, high solubility in
polar reaction systems, which thus results in separation
problems and the low thermal stability of pure HPA, has se-
verely hindered its applications. Many efforts have been
made to develop the stable water tolerant solid acid cata-
lysts. The use of this stable water tolerant solid is much eas-
ier compared to homogeneous acid catalysts.1 One way to
heterogenize HPA for use in polar media is the using of Cs+
salts of HPA, which are poorly soluble and form porous
structures.2 Another approach to improve the catalytic effi-
ciency was also made by supporting HPAs on various carri-
ers, such as ZrO2,3,4 TiO25,6 amorphous silica7,8 or a porous
supports such as zeolite Y, ordered mesoporous silica (e.g.
SBA-15 or MCM-41), or cellular foam silica.9-28 There
have been some main approaches for preparation of these
supported HPA catalysts on various carriers. One routine
way to obtain these supported HPA catalysts is the direct
impregnation of the support with a heteropoly acid solution
followed by evaporation of the solvent.12,22,29,30 Also, HPA
can be incorporated into the pores of porous material by en-
capsulating HPA during the synthesis of the silica mate-
rial.19-21,30 Perimidines are important chemical classes as a
The aim of this paper is the preparation of
H3PW12O40/NaY and H3PW12O40/NaY/MCM-41 hybrid
materials and examines the catalytic behavior the materials
towards the synthesis of perimidine.
EXPERIMENTAL
All used chemicals were purchased from Merck or
Fluka Company. Melting points were determined on an
electro thermal digital melting point apparatus. Final prod-
uct was characterized with X-Ray diffract meter (Philips
8440), radiation at room temperature (Cu-Ka), FT-IR
* Corresponding author. Tel: +988614173401 ext 2314; Fax: +988614173406; E-mail: m-zendehdel@araku.ac.ir;
mojganzendehdel@yahoo.com

684 J. Chin. Chem. Soc., Vol. 57, No. 4A, 2010
Zendehdel et al.
(Galaxy series FT-IR 5000 spectrometer) and TGA-DSC
(Rheometric scientific STA-1500 thermo gravimetric ana-
lyzer). NMR spectra were recorded on a Bruker (300 MHz)
spectrometer. Chemical shifts (ppm) were referenced to the
internal standards tetramethylsilane (TMS). Microanalyses
were performed by the Elemental Analyzer (Elemental,
Vario EL III) at the Arak University. The Microanalyses re-
sults were agreed favorably with the calculated values. Re-
actions were monitored by thin layer chromatography us-
ing silica gel F254 aluminum sheets (Merck).
from ethanol and isolated.
2-(4-Nitrophenyl)-2,3-dihydro-1H-perimidine
Orange crystals, mp 198-200 °C. IR (KBr): IR (KBr):
n = 3366, 2924, 1601, 1514, 1350 cm-1. 1H NMR (DMSO):
d (ppm) = 5.54 (s, 1H, H-2), 6.50-8.29 (m, 12H, 10CHarom
,
2NH, disapper with D2O). 13C NMR (DMSO): d (ppm):
65.3, 105.0, 112.8, 116.0, 123.9, 127.4, 129.5, 134.7,
142.5, 147.9, and 150.3. Anal calcd for C17H13N3O2: C,
70.08; H, 4.51; N, 14.43%. Found: C, 70.19; H, 4.56; N,
14.35%.
Preparation of catalysts
Synthesis of NaY and MCM-41
RESULTS AND DISCUSSION
MCM-41 prepared in our laboratory as follow by the
before method:
The synthesized catalysts, HPA/NaY and HPA/NaY/
MCM-41 hybrids, characterized by using XRD, BET,
TGA, SEM and FT-IR techniques.
A gel composite with molar composition: 1TEOS:
0.13 C19TMABr: 5.4 HCl: 150 H2O prepared and stirred at
room temperature for 7 days. After filtering and washing
with water, the catalyst characterized using XRD. The NaY
zeolite prepared and activated according to the procedure
described previously.48,49
SEM images of NaY, HPA, MCM-41 show in Fig.
1a-c. Also HPA/NaY hybrid catalysts are illustrated in Fig.
1d. It can be seen that the crystal particle size of HPA/NaY
is approximately 2 mm and we can see NaY and HPA parti-
cles with them. In the case of HPA/NaY/MCM-41 (with the
crystal size of 2 mm) as shown in Fig. 1e some rod-like ma-
terials have significant difference in the morphology of
some particles, which indicates HPA/NaY covered the ex-
ternal surface of some of MCM-41 so that rod-like MCM-
41 is not distinguished and some amorphous phase can be
observed.
Synthesis of Heteropoly acid/NaY composite
10 g H3PW12O40 mixed with 16.13 g sodium silicate
(containing 19.8 wt% SiO2 Merck), 6 mL initiator (with the
molar composition 16Na2O:Al2O3:15SiO2:320H2O and
aged at 32 °C for 32 h). Then 13.2 mL sodium hydroxide
(24 wt %) and 5.2 mL deionized water added. The mixture
then placed in an autoclave at 100 °C for 24 h. After cool-
ing the reaction mixture to room temperature, filtering,
washing with water, and drying in air, the solid product
(H3PW12O40/NaY composite) was recovered from the
mixture.
The XRD patterns of HPA, HPA/NaY, HPA/NaY/
MCM-41 hybrids and MCM-41 are presented in Fig. 2a-d.
The Fig. 2b shows the XRD pattern of HPA/NaY. Results
demonstrate that both HPA and NaY (assigned by star)
phases present as a hybrid form. As we can see, the struc-
ture of the zeolite does not collapse upon loading with the
strong heteropoly acid. Hence, the BET data show the de-
crease of the sorption capacity for NaY zeolite from 540 to
H3PW12O40/NaY/MCM-41 composites
30 g H3PW12O40/NaY hybrid added to a fresh MCM-
41 gel with the molar composition of 40SiO2:1Al2O3:
708H2O: 0.6 CTMABr and mixed with agitation to form a
H3PW12O40/NaY/MCM-41 gel, and finally placed in an au-
toclave at 100 °C for 72 h. The result solid filtered, washed
with water, calcinated at 540 °C for 6 h and then character-
ized.
Preparation of 2-(4-nitrophenyl)-2,3-dihydro-1H-
perimidine
To a solution of 1,8-naphthalenediamine (0.01 mmol)
and 4-nitrobezaldehyde (0.001 mol) in ethanol (20 mL),
0.25 g of catalyst added. The reaction mixture refluxed for
5 h at 80 °C. The used catalyst collected by filtration and
then washed with ethanol. The crude product recrystallized
Fig. 1. SEM for NaY (a), HPA (b), MCM-41 (c),
HPA/NaY (d) and HPA /NaY/MCM-41 (e).

Hybrid Heteropoly Acids
J. Chin. Chem. Soc., Vol. 57, No. 4A, 2010 685
Fig. 2. XRD for HPA (a), HPA/NaY (b), HPA/NaY/MCM-41 (c) and MCM-41 (d).
515 m2/g with the HPAloading. In addition, it also suggests
that HPA still exists within the pore channels. The XRD
patterns of HPA/NaY/MCM-41 are patterned in Fig. 2c.
The weak peak patterns with 2q ranging of 2.4 to 5 indicate
that MCM-41 structure exists as a hybrid form (Fig. 2d).
But the weak characteristic peaks of MCM-41 indexed on
(1 0 0), (1 1 0) and (2 0 0) are ascribed to the blocking effect
by impregnated HPA/NaY on the external surface. Also, in
the higher 2q region, some diffraction peaks related to NaY
and HPA with lower intensity can be observed. This de-
crease can be attributed to the pore-filling effects.50 Also, it
seems there is amorphous phase in hybrid. The MCM-41
surface area was decreased from 790 m2/g to 420 m2/g.
Based on XRD and SEM analyses, it realized that HPAmay
exists in the pore channels and on the external surface of
NaY and MCM-41. It was also seen that the significant
amount of HPA is not eliminated upon washing with sol-
vents, which may attributed to existence of a good interac-
tion between HPA and porous materials in HPA/NaY and
HPA/NaY/MCM-41 hybrids.51
FT-IR analyses conducted and the results are shown
in Fig. 3. Fig. 3(a), (b) and (c) show the spectra of raw HPA,
NaY and MCM-41, respectively. As shown in Fig. 3(a), the
absorption band near 1080 cm-1 is assigned to the asymmet-
ric stretching vibration of the central PO4 tetrahedron while
the bands near 981 cm-1, 890 cm-1 and 795 cm-1 assigned to
the stretching vibration of the WO6 octahedral. Fig. 3b
show the symmetric stretching and bending frequency
bands of Al–O–Si framework of the zeolite appear at ca.
745 and 440 cm-1, respectively.52 The FT-IR spectrum of
MCM-41 (Fig. 3c), clearly shows two characteristic bands
at 1240 cm-1 and 460 cm-1. In the FT-IR spectrum of HPA/
NaY hybrid as shown in Fig. 3(d), the intensity of charac-
teristic bands become lower, which clearly indicates the ex-
istence of HPA and NaY in the pore channels. In the case of
HPA/NaY/MCM-41 as shown in Fig. 3(e), characteristic
bands of MCM-41 near 1240 cm-1 and 460 cm-1 were ob-
served and the peaks related to NaY and HPAwith lower in-
tensity can be seen. The IR spectra of all the hybrid materi-
als showed a broad band about ca. 1009 cm-1 attributed to

686 J. Chin. Chem. Soc., Vol. 57, No. 4A, 2010
Zendehdel et al.
the asymmetric stretching of Al–O–Si chain of the zeolite.
Fig. 4a and 4b show TGA/DTA curves of HPA/NaY
and HPA/NaY/MCM-41 hybrids. The TGA/DTA of HPA/
NaY show three peaks between 25 and 800 °C, the mass
losses below 200 °C is related to dehydration of the solid
(13.14%). The HPA decomposition and condensation of
silanols in the solid (1.3670%) can be occurred at 200-600
°C. The last step can be related to the decomposition of the
zeolite structure and may be due to partial decomposition
of the acid sites. The TGA/DTA of HPA/NaY/MCM-41
show four peaks, the mass losses between 25 and 300 °C is
related to the dehydration of the solid and removal of the
surfactants incorporated into the material, due to combus-
tion or decomposition of the residual template (21.50%). In
the temperature range between 300 and 395 °C, there was
another step resulting in 2.688 wt.% weight loss, which
may be produced by the condensation of silanols in the
solid. The third step from 395 to 600 °C with 2.228%
weightless related to the decomposition of HPA. The last
step can be related to the decomposition of the structure of
zeolite and partial decomposition of the acid sites.8,53
Table 1. Catalytic activity for different catalysts
Catalyst
Yield%
HPA
07.2
25.5
05.6
72.6
68.5
NaY
MCM-41
HPA/NaY
HPA/NaY/MCM-41
Catalyst behavior
The preparation of 2-(4-nitrophenyl)-2,3-dihydro-
1H-perimidine was carried out to test the activity of cata-
lysts. Table 1 shows the following yield order for different
catalysts as HPA/NaY > HPA/NaY/MCM-41 > NaY > HPA
> MCM-41. MCM-41 exerts a very low yield, which may
ascribe to its low acid strength. The yield of reaction using
this catalyst was higher when HPA/NaY and HPA/NaY/
MCM-41 hybrids were related to the pure homogeneous
HPA. The higher activity of HPA in the composite catalyst
may be ascribed to a high dispersion of the HPA on NaY
and MCM-41, providing more protons sites on the surface
of composite than pure HPA.54 Hence, it seems that the
acidity of the NaY zeolite is effective for this reaction.
Fig. 3. FT-IR for HPA (a), NaY (b), MCM-41 (c),
HPA/NaY (d) and HPA/NaY/MCM-41 (e).
Fig. 4. TGA for HPA/NaY (a) and HPA/NaY/MCM-
41 (b).

Hybrid Heteropoly Acids
J. Chin. Chem. Soc., Vol. 57, No. 4A, 2010 687
These acid sites may be formed through the following
mechanism:
Table 2. Catalytic activity after 3 runs
Catalyst
Run
Yield%
It is well documented that heteropoly acid species in-
troduce into the channels of porous molecular sieves,
which can be easily removed when the system is treated
with polar solvents.51 However, our materials have no
leaching properties in polar solvents. In order to investiga-
tion of the catalytic activity of HPA/NaY and HPA/NaY/
MCM-41 hybrids, the catalyst was separated from the reac-
tion system by filtering and drying and followed by transfer
to the next reaction recycle. As Table 2 shows, a rather sta-
ble conversion of ~70% could be achieved after three re-
actions runs. The literature review shows that silanol OH
group on the silica surface reacts with one proton of
HPA/NaY
1
2
3
1
2
3
69.2
70.1
68.7
68.3
67.7
69.2
HPA/NaY
HPA/NaY
HPA/NaY/MCM-41
HPA/NaY/MCM-41
HPA/NaY/MCM-41
HPA/NaY and HPA/NaY/MCM-41 is changed very little
after washing with water, which indicates that heteropoly
anions were strongly bonded to the porous materials.
+
CONCLUSION
H3PW12O40 to form the SiOH2 , which creates heteropoly
-
+
anions leading to the formation of (=SiOH2 )(H2PW12O40
surface species55 of pores materials. The surface area of
)
Through this study, several conclusions have been
drawn. In the case of our synthetic method, XRD, FT-IR
Scheme I Possible mechanism for the preparation of 2-(4-nitrophenyl)-2,3-dihydro-1H-perimidine

688 J. Chin. Chem. Soc., Vol. 57, No. 4A, 2010
Zendehdel et al.
53.
and SEM indicate that some of HPA exists on the external
surface of HPA/NaY and HPA/NaY/MCM-41 even after
washing with water. BET and XRD show the pore particles
are blocked by HPA. The preparation of 2-(4-nitrophen-
yl)-2,3-dihydro-1H-perimidine was carried out to test of
these catalysts. Results exhibited higher yields with use of
HPA/NaY and HPA/NaY/MCM-41. The formation of per-
imidine was affected by the pores diameter and the Bronsted
acidity of the catalysts.
19. Shi, C.; Wang, R.; Zhu, G.; Qiu, S.; Long, J. Eur. J. Inorg.
Chem. 2005, 4801.
20. Yang, L.; Qi, Y.; Yuan, X.; Shen, J.; Kim, J. J. Mol. Catal. A
2005, 229, 199.
21. Shi, C.; Wang, R.; Zhu, G.; Qiu, S.; Long, J. Eur. J. Inorg.
Chem. 2006, 3054.
22. Zhang, J.; Ohnishi, R.; Kamiya, Y.; Okuhara, T. J. Catal.
2008, 254, 263.
23. Bordoloi, A.; Lefebvre, F.; Halligudi, S. B. J. Catal. 2007,
247, 166.
Received April 13, 2010.
24. Kozhevnikov, I. V.; Sinnema, A.; Jansen, R. J. J.; Pamin, K.;
van Bekkum, H. Catal. Lett. 1995, 30, 241.
25. Pizzio, L. R.; Vázquez, P. G.; Cáceres, C. V.; Blanco, M. N.
Appl. Catal., A. 2003, 256, 125.
REFERENCES
1. Izumi, Y.; Ogawa, M.; Urabe, K. Appl. Catal., A 1995, 132,
127.
26. Wang, J.; Zhu, H. O. Catal. Lett. 2004, 93, 209.
27. Sulikowski, B.; Rachwalik, R. Appl. Catal., A 2003, 256,
173.
2. Misono, M. Chem. Commun. 2001, 1141.
3. Devassy, B.; Halligudi, S. B.; Hegde, S. G.; Halgeri, A. B.;
Lefebvre, F. Chem. Commun. 2002, 1074.
28. Wang, J.; Lin, Z.; Han, S. Y.; Eum, M.; Lee, C. W. J. Ind.
Eng. Chem. 2003, 9, 281.
4. Sunita, G.; Devassy, B. M.; Vinu, A.; Sawant, D. P.;
Balasubramanian, V. V.; Halligudi, S. B. Catal. Commun.
2008, 9, 696.
29. Molnar, A.; Keresszegi, C.; Torok, B. Appl. Catal., A 1999,
189, 217.
30. Gagea, B. C.; Lorgouilloux, Y.; Altintas, Y.; Jacobs, P. A.;
Martens, J. A. J. Catal. 2009, 265, 99-108.
31. Pozharskii, A. F.; Dalnikovskaya, V. V. Russ. Chem. Rev.
1981, 50, 816.
5. Kumbar, S. M.; Lefebvre, F.; Halligudi, S. B. J. Mol. Catal.
A: Chem. 2006, 256, 324.
6. Waghmare, N. G.; Kasinathan, P.; Amrute, A.; Lucas, N.;
Halligudi, S. B. Catal. Commun. 2008, 9, 2026.
7. Marme, F.; Coudurier, G.; Védrine, J. C. Microporous and
Mesoporous Mater. 1998, 22, 151.
32. Deady, X.; Bu, L. W.; Finlay, G. J.; Baguley, B. C.; Denny,
W. A. J. Med. Chem. 2001, 44, 2004.
33. Caliendo, G.; Carlo, R.; Meli, R.; Perissutti, E. Eur. J. Med.
Chem. 1993, 28, 969.
8. Izumi, Y.; Ono, M.; Kitagawa, M.; Yoshida, M.; Urabe, K.
Microporous Mater. 1995, 5, 255.
34. Vinot, N. Compt. Rend. 1961, 252, 899.
35. Wiley, R. H.; Irick, G. J. Org. Chem. 1961, 26, 593.
36. Yavari, I.; Jahani-moghaddam, M.; Adib, F.; Bijanzadeh, H.
Tetrahedron. 2002, 58, 6901.
9. Molnar, A.; Keresszegi, C.; Torok, B. Appl. Catal., A 1999,
189, 217.
10. Izumi, Y.; Hisano, K.; Hida, T. Appl. Catal., A 1999, 181,
277.
37. Hendrickson, J. B.; Hussain, M. S. J. Org. Chem. 1987, 52,
4137.
11. Mukai, S. R.; Shimoda, M.; Lin, L.; Tamon, H.; Masuda, T.
Appl. Catal., A 2003, 256, 107.
38. Vanden Eynde, J. J.; Delfosse, F.; Mayence, A.; Haverbeke,
Y. V. Tetrahedron. 1995, 51, 5813.
12. Damyanova, S.; Dimitrov, L.; Mariscal, R.; Fierro, J. L.G.;
Petrov, L.; Sobrados, I. Appl. Catal., A 2003, 256, 183.
13. Yu, S.-Y.; Wang, L.-P.; Chen, B.; Gu, Y.-Y.; Li, J.; Ding,
H.-M.; Shan, Y.-K. Chem. Eur. J. 2005, 11, 3894.
14. Rao, P. M.; Wolfson, A.; Kababya, S.; Vega, S.; Landau, M.
V. J. Catal. 2005, 232, 210.
39. Mueller-Westerhoff, U. T.; Vance, B.; Yoon, D. I. Tetrahe-
dron 1991, 47, 909.
40. Deady, L. W.; Rodemann, T. J. Heterocycicl. Chem. 1998,
35, 1417.
41. Honda, K.; Nakanishi, H.; Yabe, A. Bull. Chem. Soc. Jpn.
1983, 56, 2338.
15. Kim, H.; Jung, J. C.; Yeom, S. H.; Lee, K.-Y.; Yi, J.; Song, I.
K. Mater. Res. Bull. 2007, 42, 2132.
42. Maquestiau, A.; Berte, L.; Mayence, A.; Vanden, E. Synth.
Commun. 1991, 21, 2171.
16. Kaleta, W.; Nowinska, K. Chem. Commun. 2001, 535.
17. Tarlani, A.; Abedini, M.; Nemati, A.; Khabaz, M.; Amini, M.
M. J. Colloid Interf. Sci. 2006, 303, 32.
43. Popp, F. D.; Catala, A. J. Heterocycl. Chem. 1964, 1, 108.
44. Mobinikhaledi, A.; Zendehdel, M.; Hasanvand Jamshidi, F.
Synth. React. Inorg. Met.-Org. Chem. 2007, 37, 175.
18. Hamad, H.; Soulard, M.; Lebeau, B.; Patarin, J.; Hamiek, T.;
Toufaily, J.; Mahzoul, H. J. Mol. Catal. A: Chem. 2007, 278,

Hybrid Heteropoly Acids
J. Chin. Chem. Soc., Vol. 57, No. 4A, 2010 689
45. Mobinikhaledi, A.; Foroughifar, N.; Karimi, G.; Foroughifar,
N. Synth. React. Inorg. Met.-Org. Chem. 2007, 37, 279.
46. Zendehdel, M.; Mobinikhaledi, A.; Hasanvand Jamshidi, F.
J. Incl. Phenom. Macrocycl. Chem. 2007, 59, 41.
B. Phys. E. 2008, 40, 684.
51. Kim, Y. C.; Jeong, J. Y.; Hwang, J. Y.; Kim, S. D.; Yi, S. C.;
Kim, W. J. J. Mem. Sci. 2008, 325, 252.
52. Barrer, R. M. Hydrothermal Chemistry of Zeolite; Academic
Press: New York, 1982.
47. Zendehdel, M.; Mobinikhaledi, A.; Asgari, A. J. Incl.
Phenom. Macrocycl. Chem. 2008, 60, 353.
53. Wang, J. A.; Chen, L. F.; Noren, L. E.; Navarrete, J. Appl.
Catal., A 2009, 357, 223.
48. Breck, D. W.; Tonawanda, N. Y. US Patent 3,130,007, April
21, 1964.
54. Verhoef, M. J.; Kooyman, P. J.; Peters, J. A.; van Bekkum, H.
Microporous Mesoporous Mater. 1999, 27, 365.
55. Lefebvre, F. J. Chem. Soc. Chem. Commun. 1992, 756.
49. Tanev, P. T.; Pinnavaia, T. J. Chem. Mater. 1996, 8, 2068.
50. Sohrabnezhad, Sh.; Pourahmad, A.; Sadjadi, M. S.; Sadeghi,