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Nitration of Durene and Pentamethylbenzene with Nitronium Salts in Nitromethane and Acetonitrile
Author(s) -
Hunziker E.,
Penton J. R.,
Zollinger H.
Publication year - 1971
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19710540735
Subject(s) - chemistry , nitration , nitromethane , durene , nitrous acid , protonation , photochemistry , acetonitrile , ion , nitrobenzene , organic chemistry , medicinal chemistry , inorganic chemistry , catalysis
Nature and proportions of the products formed in the nitrations mentioned in the title are affected by the process of mixing. Pentamethylnitrobenzene, formed initially in the nitration of pentamethylbenzene, is attacked by a nitronium ion at a position meta to the nitro‐group. In the σ‐complex formed, loss of a proton from a methyl group leads to production of by‐products and release of nitrite ions. The nitrous acid formed is protonated, and water is displaced from the nitrous acidium ion by the anion, PF 6 ⊖ , giving the nitrosonium ion which forms a 1:1 symmetric molecular complex with pentamethylbenzene. A similar complex is formed in the reaction between durene and nitronium salts. The results are consistent with the view that no σ‐bond is formed between the aromatic compound and the nitrosonium ion.