Nitration of phenolic compounds and oxidation of hydroquinones
67
8. Bahulayan D, Narayan G, Sreekumar V and Lalitham-
bika M 2002 Synth. Commun. 32 3565
9. Heravi M M, Bakhtiari K, Benmorad T, Bamoharram F
F, Oskooie H A and Tehrani M H 2007 Monatsh. Chem.
138 449
10. Kamal A, Kumar B A, Arifuddin M and Patrick M 2004
Ultrasonics Sonochemistry 11 455
11. Shi M, Cui S C and Yin W P 2005 Eur. J. Org. Chem.
2379
nitro compounds were not produced. We observed that
hydroquinone was oxidized with TBAD in CH2Cl2
under reflux conditions in 10 min and p-benzoquinone
was obtained with 95% isolated yield (scheme 2).
Also, in the presence of TBAC, hydroquinone was
converted to the p-benzoquinone in CH2Cl2 under
reflux conditions with 98% isolated yield.
As shown in table 2, substituted hydroquinones
(entries 2–5), 1,2-dihydroxy benzene (entry 6), 4-
methoxy phenol (entry 7), and 2-hydroxy-5-amino-
benzoic acid (entry 8) were efficiently oxidized by
12. Mallick S and Parida K M 2007 Catal. Commun. 8 1487
13. Heal M R, Harrison M A J and Cape J N 2007
Atmospheric environment 41 3515
TBAD and TBAC to the corresponding quinones with 14. Rodrigues J A R, deOliveira Fiho A P, Moran P J S and
Custodio R 1999 Tetrahedron 55 6733
15. Mellor J M, Mittoo S, Parkes R and Millar R W 2000
Tetrahedron 56 8019
high yields. In the case of 4-methoxy phenol, demethy-
lation followed by oxidation afforded benzoquinone.
16. Zolfigol M A, Bagherzadeh M, Madrakian E, Ghaemi E
and Taqian-Nasab A 2001 J. Chem. Res.140
17. Zolfigol M A, Ghaemi E and Madrakian E 2001
Molecules 6 614
18. Muathen H A 2003 Molecules 8 593
19. Vione D, Maurino V, Minero C and Pelizzetti E 2004
Chemosphere 55 941
20. Sun H B, Hua R and Yin Y 2005 J. Org. Chem. 70 9071
21. Bose A K, Ganguly S N, Manhas M S, Rao S, Speck J,
Pekelny U and Pombo-Villars E 2006 Tetrahedron Lett.
47 1885
4. Conclusion
In conclusion, efficient and selective mononitration of
structurally different phenolic compounds was per-
formed using sodium nitrite in the presence of TBAD
and TBAC under non-acidic and aprotic conditions.
High yields, mildness and good handling of the reagents
are other advantages of this method. Also, oxidation of
dihydroxy benzenes was performed in short times with
TBAD or TBAC to afford the quinones.
22. Selvam J J P, Suresh V, Rajes K, Reddy S R and
Venkateswarlu Y 2006 Tetrahedron Lett. 47 2507
23. Anuradha V, Srinivas P V, Aparna P and Rao J M 2006
Tetrahedron Lett. 47 4933
24. Shackelford S A, Anderson M B, Christie L C, Goetzen
T, Guzman M C, Hananel M A, Kornreich W D, Li H,
Pathak V P, Rabinovich A K, Rajapakse R J, Truesdale
L K, Tsank S M and Vazir H N 2003 J. Org. Chem. 68
267
Acknowledgement
Financial support by Damghan University Research
Council is gratefully acknowledged.
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