S. Gowda, D. C. Gowda / Tetrahedron 58 '2002) 2211±2213
2213
6. Prajapathi, D.; Borah, H. N.; Sandhu, J. S.; Ghosh, A. C.
Synth. Commun. 1995, 25, 4025.
hydrogenolysable substituents except the nitrile group. The
yields are virtually quantitative and the compounds obtained
are analytically pure. The obvious advantages of the
proposed method over previous methods are: *i) selective
reduction of nitro and nitrile compounds, in the presence of
other reducible or hydrogenolysable groups, *ii) easy to
operate, *iii) rapid reduction, *iv) high yields of substituted
amines, *v) avoidance of strong acid media, *vi) no require-
ment for pressure apparatus and *vii) inexpensive. This
procedure will therefore be of general use, especially in
the cases where rapid, mild and selective reduction is
required. Further investigations of other useful applications
related to the deblocking of protecting groups in peptide
synthesis are in progress.
7. Banik, B. K.; Barakat, K. J.; Wagle, D. R.; Manhas, M. S.;
Bose, A. K. J. Org. Chem. 1999, 64, 5746.
8. Akita, Y.; Inaba, M.; Uchida, H.; Ohta, A. Synthesis 1977,
792.
9. Borah, H. N.; Prajapathi, D.; Sandhu, J. S.; Ghosh, A. C.
Tetrahedron Lett. 1994, 35, 3167.
10. George, J.; Chandrashekaran, S. Synth. Commun. 1983, 13,
495.
11. Gowda, D. C.; Mahesha, B. Synth. Commun. 2000, 30, 3639.
12. Gowda, D. C.; Gowda, A. S. P.; Baba, A. R.; Gowda, S. Synth.
Commun. 2000, 30, 2889.
13. Akita, A.; Inaba, M.; Uchida, H.; Ohta, A. Synthesis 1977,
792.
14. Borah, H. N.; Prajapathi, D.; Sandhu, J. S.; Ghosh, A. C.
Tetrahedron Lett. 1994, 35, 3163.
2. Experimental
15. Romas, M. N.; Srivastva, R. M.; Brito, M. B.; De Sa, G. F.
J. Chem. Res. 'S) 1984, 228.
Hydrazinium monoformate was prepared by slowly
neutralizing equal moles of hydrazine hydrate and 85%
formic acid in an ice water bath, with constant stirring.
The hydrazinium monoformate solution thus obtained was
used as such for reduction. A suspension of an appropriate
nitrocompound or nitrile *5 mmol) and Raney nickel
*100 mg) in methanol or in any suitable solvent *3 mL)
was stirred under nitrogen atmosphere with hydrazinium
monoformate *2 mL), at room temperature. The reaction
was exothermic and effervescent. After the completion of
reaction *monitored by t.l.c.), the reaction mixture was
®ltered through celite. The organic layer was evaporated
and the residue was dissolved in chloroform or dichloro-
methane or ether was washed with saturated sodium
chloride solution to remove excess of hydrazinium mono-
formate. The organic layer after drying and evaporation
gave the desired amino derivative.
16. Finkbeiner, H. L.; Stiles, M. J. Am. Chem. Soc. 1963, 85, 616.
17. Stiles, M.; Finkbeiner, H. L. J. Am. Chem. Soc. 1959, 81, 505.
18. House, H. O. Modern Synthetic Reactions; 2nd ed; Benjamin:
New York, 1977; p 145.
19. Rylander, P. N. Hydrogenation Methods; Academic: New
York, 1985; p 365.
20. Popp, F. D.; Schultz, H. P. Chem. Rev. 1962, 62, 19.
21. Harmon, R. E.; Gupta, S. K.; Brown, D. J. Chem. Rev. 1972,
72, 21.
22. Johnson, R. A. W.; Wilby, A. H.; Entwistle, I. D. Chem. Rev.
1985, 85, 129.
23. House, H. O. Modern Synthetic Reactions; 2nd ed; Benjamin:
New York, 1977; pp 1±44.
24. Balcom, D.; Furst, A. J. Am. Chem. Soc. 1953, 75, 4334.
25. Moore, R. E.; Furst, A. J. Org. Chem. 1958, 23, 1504.
26. Brown, R. K.; Nelson, N. A. J. Am. Chem. Soc. 1954, 76,
5149.
27. Furst, A.; Moore, R. E. J. Am. Chem. Soc. 1957, 79, 5492.
28. Leggeter, B. E.; Brown, R. K. Can. J. Chem. 1960, 38, 2363.
29. Ayyanger, N. R.; Lugade, A. G.; Nikrad, P. V.; Sharma, V. K.
Synthesis 1981, 640.
In order to get a good yield of volatile aliphatic amines, the
reaction was carried out by controlled addition of hydra-
zinium monoformate, through the top of a condenser
circulated with ice water and by immersing the reaction
¯ask in a cold-water bath. After ®ltration, the whole reaction
mixture was neutralized with HCl. The solvent was evapo-
rated under reduced pressure. The residue was lyophilized
or subjected to column chromatography. Aliphatic amines
were obtained as their hydrochloride salts up to 80% yield.
30. Monti, D.; Gramatica, P.; Speranza, G.; Mannito, P.
Tetrahedron Lett. 1983, 24, 147.
31. Furst, A.; Berlo, R. C.; Hooton, S. Chem. Rev. 1965, 65, 51.
32. Ochini, E.; Mitarashi, H. Chem. Pharm. Bull., Tokyo 1963, 11,
1084.
33. Brieger, G.; Nestrick, T. J. Chem. Rev. 1974, 74, 67.
34. Brown, G. R.; Foubister, A. J. Synthesis 1982, 1036.
35. Cortese, N. A.; Heck, R. F. J. Org. Chem. 1977, 42, 3491.
36. Entwistle, I. D.; Johnstone, R. A. W.; Povall, T. J. J. Chem.
Soc., Perkin Trans. 1 1975, 1300.
References
1. Ram, S.; Ehrenkaufer, R. E. Tetrahedron Lett. 1984, 25, 3415.
2. Yuste, F.; Saldana, M.; Walls, F. Tetrahedron Lett. 1982, 23,
147.
37. Hirashima, T.; Manabe, O. Chem. Lett. 1995, 259.
38. Vogel, A. I. In Text Book of Practical Organic Chemistry;
Furniss, B. S., Hannaford, A. J., Smith, P. W. G., Tatchell,
A. R., Eds.; 5th ed, Addison-Wesely/Longman: UK, 1997;
pp 1298±1398, Chapter 10.
3. Lyle, R. E.; LaMattina, J. L. Synthesis 1974, 726.
4. Ho, T. L.; Wang, C. M. Synthesis 1974, 45.
5. Baik, W.; Han, J. L.; Lee, K. C.; Lee, N. H.; Kim, B. H.; Hahn,
J. T. Tetrahedron Lett. 1994, 35, 3965.
39. The Merck Index; Budavari, S., Ed.; 11th ed, Merck: Rahway,
NJ, 1989; p 3247.