Paper
RSC Advances
nitrile group through its p-electron-cloud which assist to acti-
vate C–N functionality to form intermediate [A] for nucleophilic
addition with NaN3, which generates the intermediate [B]. The
reaction proceeds via (3 + 2) cycloaddition between the C–N
bond of nitrile and NaN3. The complex [B] rearranges to
produce more stable [C] which on protonolysis by 35% HCl (pH
of solution was adjusted in between 2 and 3) affords the desired
product 5-substituted 1H-tetrazole and Au(III) at the end of the
reaction. Similar mechanism is expected for Au(0) nanoparticle
catalysed reaction, the enhanced reactivity of Au nanoparticles
might be due to large surface area which facilitates more
coordination between C–N of nitrile and Au(0).
Acknowledgements
Satyanand Kumar and Arvind Kumar are thankful to the UGC,
New Delhi, India for award of JRF. AA is thankful to the UGC,
New Delhi, India and Banaras Hindu University, Varanasi, for
nancial support. SKA is thankful to the University of Delhi,
Delhi for nancial assistance. Authors are also thankful to A. S.
Nagpure and Dr Satyanarayana Chilukuri for ICP analysis and
Dr Kashinath Patil, NCL Pune, India for providing XPS facility.
Notes and references
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5. Conclusions
We developed a newer highly efficient method for the synthesis
of 5-substituted 1H-tetrazoles by treatment of sodium azide
with various functionalized nitriles. This functionalization of
nitriles was achieved by using auric chloride in gold(III) state
and gold nanospheres as gold(0) state for catalysis. In addition
to aromatic and heteroaromatic tetrazole synthesis, the
protocol is found working efficiently for the aliphatic tetrazoles
synthesis with good yield, which shows its superiority over other
previously reported procedures. In the previously reported
cases, low loading of the gold catalyst is sufficient for catalysis
and the requirement of short reaction time is competitive with
the cost-effective alternatives. The signicant advantages of this
methodology include simple work-up procedure, easy prepara-
tion and handling of the catalyst, high yields, elimination of
dangerous and harmful hydrazoic acid formation and no
column chromatography of the nal product. This report may
open a new avenue of reactivity in synthetic organic chemistry.
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X-ray crystallographic study
X-Ray data were collected on Crysalis PRO (Oxford Diffraction,
2009) with graphite mono75 chromate MoKa radiation (l ¼
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ꢀ
0.71073 A) at 298(2) K. The structure was solved by a direct
method using SHELXL-97 and rened by full matrix least-
squares method on F2 (SHELXL-97).12b Crystal data for shelxl:
9 G. Wang, B. Sun and Z. Ru, Synth. Commun., 2008, 38, 3577.
ꢀ
C9H10N4, M ¼ 174.21, monoclinic, a ¼ 7.8232(8) A, b ¼ 10 Z. P. Demko and K. B. Sharpless, Org. Lett., 2001, 3, 4091.
ꢀ
ꢀ
ꢀ
ꢀ
11.9434(14) A, c ¼ 9.8716(9) A, a ¼ 90.00 , b ¼ 96.825(8) , g ¼ 11 (a) R. J. Herr, Bioorg. Med. Chem., 2002, 10, 3379; (b)
ꢀ3
ꢀ
90.00 , V ¼ 915.82(17) A , T ¼ 298(2) K, space group P21/c, Z ¼ 4,
m(MoKa) ¼ 0.082 mmꢁ1, 6368 reections measured, 1788
A. J. A. Cobb, D. A. Longbottom, D. M. Shaw and S. V. Ley,
Chem. Commun., 2004, 1808.
independent reections (Rint ¼ 0.0221). The nal R1 values was 12 J. Zabrocki, G. D. Smith, J. B. Dunbar Jr, H. Iijima and
0.0619 (I > 2s(I)). The nal wR(F2) values was 0.1981 (I > 2s(I)).
G. R. Marshall, J. Am. Chem. Soc., 1988, 110, 5875.
The nal R1 values was 0.0734 (all data). The nal wR(F2) values 13 (a) Z. P. Demko and K. B. Sharpless, Angew. Chem., Int. Ed.,
was 0.2061 (all data). The goodness of t on F2 was 1.450.14b
Crystal data for shelxl: C9H10N4, M ¼ 174.21, monoclinic, a ¼
2002, 41, 2110; (b) J. X. Y. Luo, L. L. Zhao, C. H. Wang and
J. S. Wu, Inorg. Chem. Commun., 2013, 31, 23.
ꢀ
ꢀ
ꢀ
ꢀ
14.907(2) A, b ¼ 4.9488(5) A, c ¼ 12.804(2) A, a ¼ 90.00 , b ¼ 14 Z. P. Demko and K. B. Sharpless, J. Org. Chem., 2001, 66,
ꢀ3
ꢀ
ꢀ
108.31(2) , g ¼ 90.00 , V ¼ 896.8(2) A , T ¼ 298(2) K, space group
7945.
P21/c, Z ¼ 4, m(MoKa) ¼ 0.084 mmꢁ1, 4341 reections 15 G. Aridoss and K. K. Laali, Eur. J. Org. Chem., 2011, 6343.
measured, 2427 independent reections (Rint ¼ 0.0312). The 16 (a) Y. Tang, G. Wang, Q. Ye, R. Xiong and R. Yuan, Cryst.
nal R1 values were 0.0759 (I > 2s(I)). The nal wR(F2) values
were 0.2288 (I > 2s(I)). The nal R1 values was 0.1224 (all data).
Growth Des., 2007, 7, 2382; (b) B. Li, S. Chen, Z. Chen,
J. Chen, J. Guo and L. Liu, CrystEngComm, 2011, 13, 6610.
The nal wR(F2) values was 0.2931 (all data). The goodness of t 17 R. J. Hert, Bioorg. Med. Chem., 2002, 10, 3379.
on F2 was 0.923.
18 R. Huisge, J. Org. Chem., 1968, 33, 2291.
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