A question came up in our worksheet to predict the reaction product of nitrous acid and concentrated nitric acid with benzene.
I quickly recognized it to be similar to the nitration reaction. Following this ChemGuide page, which gives the reaction of sulphonation as:
HNOX3+2HX2SOX4⟶NOX2X++2HSOX4X−+HX3OX+
I wrote this reaction:
HNOX2+2HNOX3⟶NOX++2NOX3X−+HX3OX+
and thought that this electrophilic NOX+ would then perform EAS on the benzene to give nitrosobenzene (aka nitrosation reaction).
However, the answer given in my worksheet is nitrobenzene instead. I am unsure if the following reaction (for the generation of the electrophile NOX2X+):
HNOX3+2HNOX2⟶NOX2X++NOX2X−+HX3OX+
is even valid. To me, reaction 1 seems more favorable because it involves the formation of the more stable NOX3X−. Then why is reaction 2 favored instead? Why is nitrobenzene the product of this reaction, and not nitrosobenzene?
Answer
You were absolutely correct when you said that nitrosation takes place.
What actually happens is that after nitrosation occurs, concentrated HNOX3 oxidises the nitroso group to form nitrobenzene.
Source
A Guidebook To Mechanism In Organic Chemistry; Chapter 6, section 6.2;Peter Sykes
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