TransWikia.com

Why is 4-hydroxypyridine more acidic than benzoic acid?

Chemistry Asked by user91457 on November 25, 2021

4-hydroxypyridine (or 4-pyridone) has a $mathrm{p}K_mathrm{a}$ in the ballpark of $3$ to $3.33:^1$ (in the pdf linked below, the $mathrm{p}K_mathrm{a}$ of 1-methyl-4-pyridone has been given to be $3.33$, however I suppose removing a methyl would only cause a slight decrease in the $mathrm{p}K_mathrm{a}$ value). This seems an unexpectedly low value to me. 4-pyridone seems more acidic than I expected it to be, since the $mathrm{p}K_mathrm{a}$ of other common acids are:$:^2$

begin{array}{lr}
hline
mathrm{Acid} & mathrm{p}K_mathrm{a} \
hline
text{Benzoic acid} & 4.20 \
text{Formic acid} & 3.75 \
text{Acetic acid} & 4.75\
text{Phenol} & 10.0 \
text{Carbonic acid} & 6.37rlap{:^1} \ hline
end{array}

Now I had expected 4-hydroxypyridine to be more acidic than phenol, because of the negative charge in the former’s conjugate base being delocalised onto the electronegative nitrogen, yielding a more stable resonating structure than the latter’s corresponding resonating structure. I thought that 4-pyridone’s $mathrm{p}K_mathrm{a}$ might be somewhere around $ce{H2CO3}$‘s $mathrm{p}K_mathrm{a}$, but I was wrong. Also, I wasn’t quite sure that it would be acidic enough to have a $mathrm{p}K_mathrm{a}$ value any close to other carboxylic acids. But it seems to me that it is more acidic than benzoic acid, formic acid and acetic acid.

Why is this so? I can’t see any excetional characteristic in its structure which might impart it such a low $mathrm{p}K_mathrm{a}$. This does seem more of an exception to me, as of now, but it would be very helpful if someone clarified and explained such a trend.

References:

$[1]:$ http://gissmo.nmrfam.wisc.edu/static/pKa_compilation_R_Williams.pdf

$[2]:$ https://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/acidity2.htm

2 Answers

First of all let us examine the structural formula of 4-pyridone:

4-pyridone and its tautomer

Now, as you can see, when it acts as an acid a negative charge forms on the nitrogen atom. This negative charge is well stabilized as it undergoes extensive resonance which includes oxygen as well. The fact that the negative charge is formed on nitrogen also contributes to the acidity.

Answered by Sidharth S Ghosh on November 25, 2021

The following are two resonance forms of 4-pyridone,

resonance-forms-of-4-pyridone

So, when 4-pyridone gets de-protonated, the negative charge on nitrogen gets delocalised on more electronegative atom i.e., oxygen, resulting in more stable resonance structure!

Note that, this explanation is identical to that one which is given when we compare $mathrm pK_{mathrm a}$ of benzoic acid and phenol.

Ref: Stability of 4-pyridone vs 4-pyridinol

Answered by Rahul Verma on November 25, 2021

Add your own answers!

Ask a Question

Get help from others!

© 2024 TransWikia.com. All rights reserved. Sites we Love: PCI Database, UKBizDB, Menu Kuliner, Sharing RPP