Abstract
IN 1939, Baddeley1 presented a brief survey of reactions which might be interpreted in terms of steric inhibition of resonance. Because of the lack of quantitative studies, some of the examples reported there, such as the diacetylation and the “extraordinarily facile” dinitration of mesitylene, could be considered only as suggestive hypotheses. Although no further work has appeared in support of these hypotheses2, Baddeley's interpretations of the reactions of non-coplanar substituted mesitylenes are still being considered as essentially valid in several text-books. This is surprising, because, first, in a substituted mesitylene further nuclear substitution can only occur meta to the 2-substituent already present, with no more than a secondary resonance effect3,4; and because in electrophilic substitutions conjugation of electron-withdrawing groups (NO2, COMe, etc.) with the ring is not enhanced by polarization in the transition state5.
Similar content being viewed by others
Article PDF
References
Baddeley, Nature, 144, 444 (1939).
However, some experiments from this laboratory have been discussed by me in Gazz. chim. ital., 83, 911 (1953).
de la Mare and Vernon, J. Chem. Soc., 1764 (1951).
Illuminati and Marino, J. Amer. Chem. Soc., 78, 4975 (1956).
Ingold, “Structure and Mechanism in Organic Chemistry”, 247 and 252 (Bell, London, 1953).
Illuminati and Palmucci Illuminati, J. Amer. Chem. Soc., 75, 2159 (1953).
Ingham and Hampson, J. Chem. Soc., 981 (1939). Hammick, New and Williams, ibid., 29 (1934). Brown, de Bruyne and Gross, J. Amer. Chem. Soc., 56, 1291 (1934).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
ILLUMINATI, G. Non-Coplanarity of the Nitro Group and Rate of Electrophilic Substitution in Nitromesitylene. Nature 179, 780 (1957). https://doi.org/10.1038/179780a0
Issue Date:
DOI: https://doi.org/10.1038/179780a0
Comments
By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.