Master Organic Chemistry Reaction Guide

Sulfonylation of Arenes to give sulfonic acids

Description: Treatment of an aromatic molecule such as benzene with sulfur trioxide and a strong acid leads to formation of sulfonic acids.
Content available for Reactionguide members only. Not a member? Get access for about 30 cents / day!

Comments

Comment section

9 thoughts on “Sulfonylation of Arenes to give sulfonic acids

  1. Wonderful. Thank you. Electron withdrawing due to the electronegative oxygens, and the fact that the Pi orbitals are not the same size? Would it be useful as an instigator for addition-elimination nucleophilic aromatic substitution? (the same way that NO2 is?)

    1. It’s not easy to do – but it happens. It’s much more difficult to perform this reaction on benzene than on an ordinary alkene. It’s usually important to heat this reaction.

  2. Since HSO4- is the conjugate base of a strong acid, how does it strong enough of a base to eliminate the proton (Step 3) to reform the aromatic benzene? I have seen a similar but different mechanism for this reaction that avoids this problem by initially having the pi bond attack SO3 rather than SO3H, resulting in an anion, at which point water acts as a base deprotonating to reform the aromatic system. This water is now a hydronium ion which is used to protonate the SO3- to become SO3H. How do I know which of these two mechanisms is correct?

    1. The proton in question is extremely acidic as its conjugate base is quite stable (it’s aromatic).

      If neutral water is present, then yes, neutral water would likely act as the base here.

      Protonation of SO3 to give SO3H+ accelerates the reaction considerably. The rate limiting step is not deprotonation, but attack of the benzene ring on sulfur.

Leave a Reply

Your email address will not be published. Required fields are marked *

This site uses Akismet to reduce spam. Learn how your comment data is processed.