Selective Hydration of Nitriles to Amides Over Titania Supported Palladium Exchanged…
Table 6 Recycling results of
20 % PdMPAV1/TiO2 catalyst
No. of recycles
Nitrile conversion (%)
Amide yield (%)
Acid yield (%)
Fresh
100
97.0
95.2
94.8
94.5
3.0
3.0
1.6
1.3
1
2
3
98.2
96.4
95.8
Reaction conditions Nitrile: 1 mmol, Water 3 ml, Catalyst 80 mg, Reaction temperature 140 °C
5. Kukushkin VY, Pombeiro AJL (2002) Chem Rev 102:1771
6. Kroschwitz J (1991) Encyclopedia of polymer science and
engineering. Wiley, New York
7. Bailey PD, Mills TJ, Pettecrew R, Price RA (2005) Compre-
hensive organic functional group. Transformations II 5:201
8. Valeur E, Bradley M (2009) Chem Soc Rev 38:606
9. Wang G, Yu Q-Y, Chen S-Y, Yu X-Q (2014) Org Biomol Chem
12:414
10. March J (1992) Advanced organic chemistry. Wiley-Interscience,
New York, p 383
11. Shimizua KI, Imaiidab N, Sawabeb K, Satsuma A (2012) Appl
Catal A 114:421
Table 6. The amide yield after three cycles was almost same
and these results suggest that the catalyst is reusable with
consistent activity. The fresh and reused catalyst was char-
acterized by ICP-AES in order to know the leaching of any
Pd in the catalyst. The ICP-AES analysis results indicate that
there was no considerable change in the Pd content in both
fresh (2.14 %) and reused catalyst (2.08 %). This result
confirms that there was no leaching of Pd and suggests the
heterogeneous nature of the catalyst.
12. Pala Wilgus C, Downing S, Molitor E, Bains S, Pagni RM,
Kabalka GW (1995) Tetrahedron Lett 36:469
4 Conclusions
13. Moorthy JN, Singhal N (2005) J Org Chem 70:1926
14. Edward JT, Meacock SCR (2005) J Chem Soc 42:2721
15. Kukushkin VY, Pombeiro AJL (2005) Inorg Chim Acta 358:1
16. Ma X-Y, He Y, Hu Y-L, Lu M (2012) Tetrahedron Lett 53:449
17. Barbosa LAMM, Van Santen RA (2001) J Mol Catal A 166:101
18. Cadierno V, Francos J, Gimeno J (2008) Chem Eur J 14:6601
19. Leung CW, Zheng W, Zhou Z, Lin Z, Lau CP (2008) Organo-
metallics 27:4957
20. Goto A, Endo K, Saito S (2008) Angew Chem Int Ed 47:3607
21. Lee J, Kim M, Chang S, Lee H-Y (2009) Org Lett 11:5598
22. Mitsudome T, Mikami Y, Mori H, Arita S, Mizugaki T, Jit-
sukawa K, Kaneda K (2009) Chem Commun 22:3258
23. Crestani MG, Arevalo A, Garcia J (2006) Adv Synth Catal
348:732
24. Kim ES, Kim HS, Kim JN (2009) Tetrahedron Lett 50:2973
25. Schimizu KI, Kubo T, Satsuma A, Kamachi T, Yoshizawa K
(2012) ACS Catal 2:2647
26. Schimizu KI, Imaiida N, Sawabe K, Satsuma A (2012) Appl
Catal A: Gen 421:114
27. Oberhauser W, Bartoli M, Petrucci G, Bandelli D, Frediani M,
Capozzoli L, Cepek C, Bhardwaj S, Rosi L (2015) J Mol Catal A
410:26
Titania supported palladium exchanged molyb-
dovanadophosphoric acid catalysts were prepared with
intact Keggin structure. PdMPAV1/TiO2 was an efficient
catalyst for selective hydration of nitrile to amides under
mild reaction conditions. The activity of the catalyst
depends on V and Pd present in Keggin heteropoly
molybdate. This catalyst is active for the selective hydra-
tion of nitriles containing various electron donating and
electron withdrawing groups to the corresponding amides
in high yields. The hydration of nitriles activity also
depended on reaction temperature and amount of catalyst.
The catalyst is easy to recover and reusable without any
loss in activity. In the present catalyst Pd is exchanged with
the protons of MPAV1 and exists as Pd (II) and the redox
properties of V might be helping in achieving the high
activity towards the hydration of nitriles to amides.
28. Gangarajula Y, Gopal B (2014) Appl Catal A 475:211
29. Kozhevnikov IV (1998) Chem Rev 98:171
30. Okuhara T, Mizuno N, Misono M (2001) Appl Catal A 222:63
31. Srivani A, Venkateswaera Rao KT, Sai Prasad PS, Lingaiah N
(2010) J Mol Catal A 328:119
Acknowledgments B. Srinivasa Rao thanks University Grants
Commission (UGC), India for financial support in the form of Junior
Research Fellowship.
32. Tsigdinos GA, Hallada CJ (1968) Inorg Chem 7:437
33. Lingaiah N, Mohan Reddy K, Nagaraju P, Sai Prasad PS, Wachs
IE (2008) J Phys Chem C 112:8294
References
34. Casarini D, Centi G, Jiru P, Lena V, Tvaruzkova Z (1993) J Catal
143:325
35. Venkateswara Rao KT, Rao PSN, Nagaraju P, Sai Prasad PS,
Lingaiah N (2009) J Mol Catal A 303:84
36. Srivani A, Venkateswaera Rao K. T, Sai Prasad P. S, Lingaiah N
(2014) J. Chem. Sci 126:67
37. Hardcastle FD, Wachs IE (1991) J Phys Chem 95:5031
38. Muzart J (2011) J Mol Catal A 338:7
1. Thallaj NK, Przybilla J, Welter R, Mandon D (2008) J Am Chem
Soc 130:2414
2. Kim ES, Seung Lee H, Hwan Kim S, Nyoung Kim J (2010)
Tetrahedron Lett 51:589
3. Greenberg A, Breneman CM, Liebman JF (2000) The amide
linkage: structural significance in chemistry, biochemistry and
materials science. Wiley, New York
39. Ferrer I, Rich J, Fontrodona X, Rodriguez M, Romero I (2013)
Dalton Trans 42:13461
4. Garcia-Alvarez R, Crochet P, Cadierno V (2013) Green Chem
15:46
123