Sulfuric acid on silica-gel: An inexpensive catalyst for aromatic nitration

Tetrahedron Letters

Volumn 37, Issue 4, 1996, Pages 513-516

  Riego, Juan M ^a   Sedin, Zeno ^a   Zaldívar, José M ^a   Marziano, Nunziata C ^b   Tortato, Claudio ^b  

^a JOINT RESEARCH CENTRE   (Italy)

^b CA' FOSCARI UNIVERSITY OF VENICE   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

AROMATIC NITRO COMPOUND;

ARTICLE; CATALYSIS; DRUG SYNTHESIS; REACTION ANALYSIS;

EID: 0030031144     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(95)02174-4     Document Type: Article

References (30)

1. (a) Olah, G.A., Malhotra, R. Narang, S.C., "Nitration. Methods and Mechanisms", VCH Publishers: New York, 1989.
2. (b) Schofield, K., "Aromatic nitration", Cambridge University Press: Cambridge, 1980.
3. (c) Olah, G.A. and Kuhn, S.J. in "Friedel-Crafts and Related Reactions", vol. 3, Part 2, Olah G.A., Ed., Interscience, New York, 1964.
4. 12 (mesitylene): a) Marziano, N.C., Tortato, C., Sampoli, M., J. Chem. Soc. Perkin Trans. II, 1991, 423.
5. 10:
6. d) Sampoli, M., de Santis, A., Marziano N.C., Pinna, F., Zingales, A., J. Phys. Chem., 89, 2864, (1985).
7. Mainly sulfuric acid, water, organic products and oxidation by-products.
8. 3 over a polystirenesulfonic acid alone or supported on Celite: Kameo, T., Nishimura, S., Manabe, O., Nippon Kagaku Kaishi, 1, 122, (1974).
9. 3 over a sulfonated polystyrene resin: Wright, O.L., Teipel, J., Thoennes, D., J. Org. Chem., 30, 1301, (1965).
10. 2 for activated substrates as phenols or anysoles: Tapia, R., Torres, G., Valderrama, J. A. Syn. Comm., 16, 681, (1986).
11. 3 or alkyl nitrates over Nafion-H perfluorosulfonic acid resin with azeotropic removal of water: Olah, G.A., Malhotra, R. Narang, S.C., J. Org. Chem., 43, 4628, (1978).
12. 4: Milligan, B., Miller, D.G. U.S. Patent 3,957,889, 1976.
13. Nitrates of transition metals on K10 montmorillonite: (a) Laszlo, P., Acc. Chem. Res., 19, 121, (1986).
14. (b) Laszlo, P., Pennetreau P. J. Org. Chem., 52, 2407, (1987).
15. (c) Cornelis, A., Laszlo, P., Janssen Chim. Acta, 8, 3, (1990) and references therein.
16. 3 for anysoles: Nagy, S.M., Zubkov E.A., Shubin, V.G., Pelmenshikov, A.G., Paukshtis E.A., Razdobarova, N.L., Acta Chim. Hung., 129(5), 579, (1992).
17. Reviews on reagents on inorganic supports see: (a) Mc Killop, A., Young, D.W., Synthesis 1979, 401.
18. (b) Posner, G.H., Angew. Chem. Int. Ed. Engl., 17, 487, (1978).
19. (c) Laszlo, P. Ed., "Preparative Chemistry Using Supported Reagents", Academic Press Inc., London, 1987. For polymeric supports, see references in Olah, G.A., Iyer, P.S., Prakash, G.K.S., Synthesis, 1986, 513.
20. (c) Laszlo, P. Ed., "Preparative Chemistry Using Supported Reagents", Academic Press Inc., London, 1987. For polymeric supports, see references in Olah, G.A., Iyer, P.S., Prakash, G.K.S., Synthesis, 1986, 513.
21. a) Costa, A., Mestres, R., Riego, J.M., Synth. Commun. 12, 1003 (1982).
22. b) Costa, A., Riego, J.M., Saá, J.M., Chem. Lett., 9, 1565 (1986).
23. c) Costa, A., Riego, J.M., Can. J. Chem., 65(10), 2327 (1987).
24. GRACE GmbH Silica Gel Catalyst Carrier 239/ 30-100 micron.
25. The total acidity was measured by thoroughly extracting an aliquot of the acidic solid with water followed by titration of the joined extracts with 0.1 N aqueous NaOH in an automated titrator.
26. 4 used. Catalysts made from sulfuric acid of concentration >70% were better handled under an inert atmosphere.
27. 4 were detected in the distillate water. The azeotrope of cyclohexane and water was used for chlorobenzene.
28. +/g), complex mixtures of mononitro, dinitro and tarry materials were obtained.
29. Oven dried at 130°C for 24 h.
30. Tanabe, K. Solid Acids and Bases their catalytic properties, Academic Press, Tokyo, 1970; pp 2-3 and references therein.