Aromatic nucleophilic substitution of hydrogen: reactions of 6-nitroquinoline with potassium cyanide and nitroalkanes

Abstract

The reactions of 6-nitroquinoline 1 and potassium cyanide with methyl nitroacetate, nitroethane, 1-nitropropane, and 2-nitropropane have been carried out in the medium of dimethyl sulfoxide. ¹H NMR has been used to identify the reaction products from 6-nitroquinoline 1 with methyl nitroacetate and potassium cyanide and to determine the proportions of products in the reaction mixture. The main reaction products are 6-(methoxalylamino)quinoline-5-carbonitrile 6 and 1-aminoisoxazolo[4,3-f  ]quinoline 9. The reactions of 6-nitroquinoline 1 with potassium cyanide and primary nitroalkanes give, as the main products, 3-substituted pyrido[3,2-f  ]quinazolin-1(2H )-ones 12a,b. The reaction of 6-nitroquinoline 1 and potassium cyanide with 2-nitropropane produces 3-(1-cyano-1-methylethyl)-2,3-dihydro-1H-pyrazolo[4,3-f  ]quinolin-1-one 14 as the chief product. In all cases the reaction involves substitution of the 5-hydrogen of quinoline skeleton with concomitant lowering of oxidation number of the nitrogen atom in the original nitro group of 1. A mechanism is suggested for the reactions investigated involving 6-nitrosoquinoline-5-carbonitrile 3 as a likely common intermediate.

References

1. A. Halama, J. Kaválek, V. Macháček and T. Weidlich, J. Chem. Soc., Perkin Trans. 1, 1999, 1839.
2. Y. Tomioka, A. Mochiike, J. Himeno and M. Yamazaki, Chem. Pharm. Bull., 1981, 29, 1286.
3. Y. Tomioka, K. Ohkubo, J. Himeno and M. Yamazaki, Chem. Pharm. Bull., 1985, 33, 1360.
4. F. Terrier, Nucleophilic Aromatic Displacement: The Influence of the Nitro Group, VCH Publishers, New York, 1991, p. 267.
5. R. Tamura, A. Kamimura and O. Noboru, Synthesis, 1991, 423.
6. N. Kornblum and P. A. Wade, J. Org. Chem., 1987, 52, 5301.
7. N. Kornblum and A. S. Ericson, J. Org. Chem., 1981, 46, 1037.
8. D. Wilbur, W. B. Manning, B. D. Hilton and G. M. Muschik, Org. Magn. Reson., 1982, 18, 63.
9. H. E. Foster and J. Hurst, J. Chem. Soc., Perkin Trans. 1, 1973, 319.
10. R. Y. Ning, P. B. Madan and L. H. Sternbach, J. Org. Chem., 1973, 38, 3995.
11. K. Sakai and J. P. Anselme, J. Org. Chem., 1972, 37, 2351.