The nitration of styrenes by nitric acid in dichloromethane

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Richard J. Lewis and Roy B. Moodie


Abstract

Kinetics and products of reaction of 4-R-styrenes (R = Me, H, Cl, CF3, NO2) with nitric acid in dichloromethane are reported. Reaction occurs in the alkene group and aromatic nitration is insignificant. With increasingly electron-withdrawing substituents the reaction changes from one which is third order in nitric acid and gives rise to the 1-arylethyl nitrate, to one which is of higher order in nitric acid and gives rise to the 2-nitro-1-arylethyl nitrate (β-nitro-nitrate). Both reactions proceed through transition states with carbocation character, by initial β-addition of H+ and NO2+ respectively. The β-nitro-nitrate is formed in part also by a radical pathway, as are other minor products.


References

  1. R. J. Lewis and R. B. Moodie, J. Chem. Soc., Perkin Trans. 2, 1996, 1315 RSC.
  2. G. A. Olah, R. Malhotra and S. C. Narang, Nitration: Methods and Mechanisms, VCH, New York, 1989 Search PubMed.
  3. A. V. Topchiev, The Nitration of Hydrocarbons and other Compounds, Akad Nauk SSSR, Moscow, English Edition, Pergamon, 1959 Search PubMed.
  4. V. V. Perekalin, E. S. Lipina, V. N. Berestovitskaya and D. A. Efremov, Nitroalkenes: Conjugated Nitro Compounds, Wiley, New York, 1994 Search PubMed.
  5. S. W. Tinsley, J. Org. Chem., 1961, 26, 4723; F. van der Lee, Recl. Trav. Chim, Pays-Bas, 1928, 47, 920.
  6. F. G. Bordwell and E. W. Garbisch, J. Org. Chem., 1963, 28, 1765 CAS.
  7. F. G. Bordwell and E. W. Garbish, J. Org. Chem., 1962, 27, 2322, 3049.
  8. F. G. Bordwell and E. W. Garbisch, J. Am. Chem. Soc., 1960, 82, 3588 CrossRef CAS.
  9. R. B. Moodie, K. Schofield and G. D. Tobin, J. Chem. Soc., Perkin Trans. 2, 1977, 1688 RSC.
  10. J. Dormer and R. B. Moodie, J. Chem. Soc., Perkin Trans. 2, 1994, 1195 RSC.
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