23
$\begingroup$

If we make a resonance structure for the anilinium ion, with positive charge at either the ortho or the para position, we get a pentavalent nitrogen, which is not possible. So, how is the $\ce{-NH3+}$ group meta-directing in electrophilic aromatic substitution reactions, e.g. in nitration of aniline under acidic conditions?

$\endgroup$
21
$\begingroup$

how is anilinium ion meta directing for electrophiles?

Actually, anilinium is not meta directing (I know it is often taught that way), but rather it inductively deactivates the entire aromatic ring.

To explain the electrophilic substitution pattern observed with any aromatic system we must consider both resonance and inductive effects.

Resonance Effects: You are correct that you can't delocalize the positive charge on the anilinium nitrogen into the benzene ring through resonance. As you point out, resonance structures with 5 bonds to nitrogen aren't allowed.

enter image description here

Therefore resonance effects are not involved in explaining the reactivity of the anilinium ion towards electrophilic aromatic substitution.

Inductive Effects: Inductively we expect the anilinium nitrogen to strongly withdraw electron density from the ortho position since it is closest to the positively charged nitrogen, this makes the ortho position the most deactivated. Inductive effects die off quickly with distance, so we would expect the meta position to also be deactivated, but less so than the ortho position. Finally, we would still expect some deactivation at the distant para position, but slightly less than we saw at the meta position. Overall, in terms of reactivity we would expect para > meta > ortho, with the difference between para and meta being much smaller than the difference between meta and ortho due to the effect distance has on inductive electron withdrawal.

If we examine the nitration of aniline in strong acid ($\ce{HNO3}$, $\ce{H2SO4}$), under these conditions the strong acid will completely protonate the aniline and reaction will proceed through the anilinium ion. We see that, as expected, there is very little ortho product and slightly more para product than meta product. This is pretty much as we expected and is consistent with the electron withdrawing inductive effect of the positive anilinium nitrogen.

enter image description here

$\endgroup$
  • 1
    $\begingroup$ Thanks for your answer! Can you please also comment on the directing nature of $\ce{-NR3+}$ (not $\ce{-NH3+}$)? Would here the inductive effects of the three alkyl groups make this group meta directing somehow? Is there experimental evidence related to this? Thanks! $\endgroup$ – Gaurang Tandon Mar 17 '18 at 13:20
  • 1
    $\begingroup$ @GaurangTandon Since what you ask is a different question from the OP, you may want to post it as a new question. I haven't searched the $\ce{Ph-NR3^{+}}$ case, but my intuition tells me that it would behave similarly to $\ce{Ph-NH3^{+}}$ $\endgroup$ – ron Mar 17 '18 at 17:27
  • 1
    $\begingroup$ No @ron, it doesn't ... (Source: March's Advanced Organic Chemistry) only $\ce{NH3+}$ is an exception rest all ($\ce{NR3+ , NHR2+}$) etc are meta directing...I am unable to rationalise this. $\endgroup$ – Abcd Mar 20 '18 at 1:19
  • $\begingroup$ @Abcd Did you happen to post a question about this exception? (And which page in March?) $\endgroup$ – Gaurang Tandon Jun 19 '18 at 4:04

Your Answer

By clicking “Post Your Answer”, you agree to our terms of service, privacy policy and cookie policy

Not the answer you're looking for? Browse other questions tagged or ask your own question.