Nitro derivatives of the thiophene series. 4. Nitration of thiophene derivatives with metal nitrates in acetic anhydride
Rent the article at a discountRent now
* Final gross prices may vary according to local VAT.Get Access
The nitration of 2-formylthiophene, 2-acetothienone, and unsaturated ketones of the thiophene series with copper and aluminum nitrates in acetic anhydride at various temperatures was studied. At low temperatures 2-acetothienone gives a mixture of 4- and 5-nitro isomers, while 2-formylthipphene gives only a 5-nitro-substituted compound in the diacetate form; α,β-unsaturated ketones are not nitrated under these conditions. When the reaction is carried out at 70–90 °C, one can obtain mixtures of nitro ketones in the case of unsaturated ketones; 2-formylthiophene is oxidized to thiophene-2-carboxylic acid, while 2-acetothienone gives a substance, the structure of which could not be established. The reaction of copper and aluminum nitrates with acetic anhydride was investigated by means of thermal and x-ray diffraction analysis. It is shown that the reaction is accompanied by the formation of free nitric acid, and the nitrating agent in these mixtures is consequently the nitronium cation.
- Yu. D. Churkin, L. V. Panfilova, A. S. Shashkov, and K. Ya. Burshtein, Khim. Geterotsikl. Soedin., No. 6, 753 (1981).
- I. J. Rinkes, Rec. Trav. Chim., 52, 538 (1933).
- J. Tirouflet and P. Fournari, Compt. Rend., 243, 61 (1956).
- V. S. Egorova, V. N. Ivanova, and N. I. Putokhin, Zh. Obshch. Khim., No. 12, 4084 (1964).
- H. Becker, Introduction to the Electronic Theory of Organic Reactions [Russian translation], Mir, Moscow (1977), p. 496.
- N. O. Saldabol and S. A. Giller, Izv. Akad. Nauk Latv. SSR, No. 10, 101 (1958).
- Yu. D. Chirkin, L. V. Panfilova, A. S. Shashkov, and K. Ya. Burshtein, Khim. Geterotsikl. Soedin., No. 3, 325 (1981).
- J. B. Menke, Rec. Trav. Chim., 44, 141 (1925).
- A. V. Zimichev and A. E. Lipkin, in: Structure and the Properties of Molecules [in Russian], Kuibyshev (1976), p. 128.
- ASTM Catalog, Nos. 24-310, 14-811, 14-687, 14-774, 17-778, and 12-472.
- The Chemist's Handbook [in Russian], Vol. 2, GNTIKhL, Leningrad-Moscow (1951), p. 19.
- C. K. Ingold, Theoretical Foundations of Organic Chemistry [Russian translation], Mir, Moscow (1973), p. 1054.
- E. Campaigne and P. Monroe, J. Am. Chem. Soc., 75, 988 (1953).
- G. N. Dorofeenko, Zh. Obshch. Khim., 31, 994 (1961).
- G. Gilman (editor), Organic Syntheses [Russian translation], Vol. 1, Moscow (1949), p. 76.
- Nitro derivatives of the thiophene series. 4. Nitration of thiophene derivatives with metal nitrates in acetic anhydride
Chemistry of Heterocyclic Compounds
Volume 17, Issue 7 , pp 673-675
- Cover Date
- Print ISSN
- Online ISSN
- Kluwer Academic Publishers-Plenum Publishers
- Additional Links
- Industry Sectors