Preparation of p-chlorobenzoic acid from p-chloronitrobenzene

Question

I was reading my book where I spotted the preparation of p-chlorobenzoic acid from p-chloronitrobenzene.

The preparation method there was given as such:

$\ce{Sn/HCl}$
$\ce{NaNO2 + HCl}$ ($\pu{0-5 ^\circ C}$)
$\ce{CuCN}$
$\ce{H2O/H+}$

Now, the thing is that, I recall the first two steps from the process of forming diazonium salts but I have never seen the last two steps give the $\ce{-COOH}$ group.

Also I recall that $\ce{CuCN}$ gives us the nucleophile $\ce{CN-}$ where the negative charge is on the nitrogen atom and also that $\ce{H2O/H+}$ is used for hydration but I don't see how these two could help us form p-chloronitrobenzene from Benzenediazonium chloride.

The reaction of CuCN with the diazonium salt is a Sandmeyer reaction. The last step is a hydrolysis of the nitrile formed in the Sandmeyer reaction. — user55119, May 31 '20 at 19:13
You recall incorrectly, the negative charge in cyanide is on the carbon — Waylander, May 31 '20 at 19:22
@user55119 But isn't the sandmeyer reaction only for halogens ,for eg NaCl and NaBr? — TheChemist, May 31 '20 at 19:40
@Waylander But isn't it of the format of AgCN where the - charge is on the N atom? — TheChemist, May 31 '20 at 19:42
No, in general cyanide is nucleophilic through carbon https://en.wikipedia.org/wiki/Cyanide — Waylander, May 31 '20 at 19:43
@Waylander But we do have Ambident nucleophiles, for eg in NaCN and KCN charge in cyanide is on carbon whereas in AgCN , charge is on nitrogen. — TheChemist, May 31 '20 at 19:48
Yes, we do. This answer explains why https://chemistry.stackexchange.com/questions/58104/why-do-sn2-reactions-of-alkyl-halides-proceed-differently-with-kcn-and-agcn but in general when you see cyanide ion - unless it is AgCN - assume that the nucleophilic reaction is through carbon. — Waylander, May 31 '20 at 20:07
CN- and NC- are different. One is called cyanide ion, other one is called isocyanide ion. Also, correct the spelling of nucleophile in your question. — Nilay Ghosh, Jun 01 '20 at 05:16
@TheChemist Please don't delete \pu{…} macro in posts. See Undefined control sequence \pu in official SE Android app. The problem doesn't lie with the macro, it's the mobile app that you are likely using that hasn't been updated for a long time. — andselisk, Jun 01 '20 at 05:26

Mathew Mahindaratne · Accepted Answer · 2020-05-31T23:00:44.910

This is simply the summery of all comments involved:

$$\ce{Cl-C6H4-NO2 ->[Sn/HCl] Cl-C6H4-NH3+Cl-} \tag1$$

$$\ce{Cl-C6H4-NH3+Cl- ->[\text{a. } NaNO2/HCl \ (\pu{0-5 ^\circ C})][\text{b. } CuCN] Cl-C6H4-CN} \\ \tag2$$

$$\ce{Cl-C6H4-CN ->[H+/H2O][\Delta] Cl-C6H4-COOH} \\ \tag3$$

Note: The reaction $(1)$ is a typical reduction reaction, which reduce nitro group to amino group. The reaction $(2)$ is called Sandmeyer Reaction. Finally, The reaction $(3)$ is a hydrolysis condition to convert cyano group to carboxylic acid group. That hydrolysis can be done under basic conditions as well (then, final product is carboxalate).

Also note that even though it is not necessary, I put this answer up just to avoid people asking same kind of questions again and again. When they have a visual answer they might not do so.

Preparation of p-chlorobenzoic acid from p-chloronitrobenzene

1 Answers1