NJC
Paper
corresponding tetrazole, due to the significant effect of the
substitute positions on the reactivity of the nitrile substrates
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(
Table 2, entry 3). 4-Methoxylbenzonitrile as substrate gave an
excellent yield of the corresponding tetrazole up to 91%
Table 2, entry 4). The electron withdrawing group substituted
nitriles such as 4-chlorobenzonitrile, 4-bromobenzonitrile and
-nitrobenzonitrile also provided good to excellent yields of the
(
4
corresponding tetrazoles (Table 2, entries 5–7), which demonstrated
that the electron withdrawing groups are able to maintain the good
reactivity of the nitriles. The highest yield of tetrazole was obtained
with 4-cyanopyridine as the substrate due to the strong electron
withdrawing effect of the pyridine groups, which evidenced the
9 D. P. Matthews, J. E. Green and A. J. Shuker, J. Comb. Chem.,
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positive effect of the electron withdrawing groups on the reactivity 10 Z. P. Demko and K. B. Sharpless, J. Org. Chem., 2001, 66,
9,44–46
(Table 2, entry 8).
It is noteworthy that the aliphatic nitrile,
7945–7950.
4
-nitro benzyl cyanide also gave a good yield of the corresponding 11 Z. P. Demko and K. B. Sharpless, Org. Lett., 2002, 4,
tetrazole (Table 2, entry 9). These results demonstrated the superior
2525–2527.
properties of WAlPO-5 as novel heterogeneous catalysts for the 12 S. Hajra, D. Sinha and M. Bhowmick, J. Org. Chem., 2007, 72,
synthesis of tetrazoles by [3+2] cycloaddition from nitriles and
sodium azide.
1852–1855.
13 D. Amantini, R. Beleggia, F. Fringuelli, F. Pizzo and
L. Vaccoro, J. Org. Chem., 2004, 69, 2896–2898.
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
4 S. Hanessian, D. Simard, B. Desch ˆe nes-Simard, C. Chenel
and E. Haak, Org. Lett., 2008, 10, 1381–1384.
5 W. K. Su, Z. Hong, W. G. Shan and X. X. Zhang, Eur. J. Org.
Chem., 2006, 2723–2726.
4
Conclusions
In conclusion, a tungsten atom-containing AlPO-5 microporous
molecular sieve was synthesized with TEA as the structure template
from pseudoboehmite, H PO and HPW. The incorporation of the
3 4
6 D. Kundu, A. Majee and A. Hajra, Tetrahedron Lett., 2009, 50,
2
668–2670.
7 J. Bonnamour and C. Bolm, Chem. - Eur. J., 2009, 15,
543–4545.
tungsten atoms into the AlPO-5 skeleton has been demonstrated by
systematic characterizations. Furthermore, the WAlPO-5 micro-
spheres can be used as an efficient heterogeneous catalyst for the
synthesis of 5-substituted 1H-tetrazoles by [3+2] cycloaddition from
nitriles and sodium azide. As a novel heterogeneous catalyst, the
WAlPO-5 microspheres exhibit a high catalytic activity, a superior
cycling stability and an excellent substrate applicability. The
significant advantages of the WAlPO-5 microspheres, such as
the simple procedure and the mild reaction conditions and
as an alternative to those corrosive, hazardous and polluting
homogeneous catalysts, warrant its potential application in
industrial processes. The further improvement in the catalytic
performances of the WAlPO-5 microspheres and the continuous-
flow reaction process will be pursued in this laboratory.
4
8 M. L. Kantam, K. B. S. Kumar and C. Sridhar, Adv. Synth.
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9 M. L. Kantam, K. B. S. Kumar and K. P. Raja, J. Mol. Catal. A:
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0 M. L. Kantam, V. Balasubrahmanyam and K. B. S. Kumar,
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Acknowledgements
Financial supports from the Talent Training Unite Fund of
NSFC-Henan (no. U1204203), the China Postdoctoral Science
Foundation (no. 2013T60705) and the Innovation Fund for
Elitists of Henan Province, China (no. 0221001200) are
acknowledged.
6 B. Sreedhar, A. S. Kumar and D. Yada, Tetrahedron Lett.,
2011, 52, 3565–3569.
7 J. H. He, B. J. Li, F. S. Chen, Z. Xu and G. Yin, J. Mol. Catal. A:
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Notes and references
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3
082 | New J. Chem., 2014, 38, 3078--3083
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