13
$\begingroup$

The Sandmeyer reaction is an extremely useful reaction for the functionalization of aromatic rings through a diazonium intermediate. For conversion of a diazonium intermediate to the corresponding chloride, bromide, or cyanide, the copper(I) salt is used. Surprisingly (to me at least) for iodination, potassium iodide is the reagent of choice, as described in Maitland Jones's Organic Chemistry (and elsewhere I'm sure), but no rationale is given. SciFinder searches also show that potassium iodide is most frequently used.

Is there something special about copper(I) iodide that makes it unsuitable for use in the Sandmeyer reaction?

|improve this question
$\endgroup$
5
$\begingroup$

Sandmeyer reactions using iodides, water, and thiols do not require the copper(I) ion as a catalyst for the reaction to proceed whereas your other nucleophiles do (though not necessarily stoichiometrically).

Sandmeyer Mechanism Sandmeyer without copper

enter image description here

As you can see the copper(I) ion is important in reducing the diazonium to nitrogen and forming a radical. Iodine, oxygen, and sulfur must be able to be oxidized by diazonium and therefore do not require copper.

|improve this answer
$\endgroup$
  • $\begingroup$ Is there any evidence that thiols, water (and presumably alcohols), and iodide are oxidized? Oxidation of thiols and iodide are (relatively) facile, but I don't consider oxidation of water to be in the same class. If it has something to do with nucleophilic strength, surely cyanide is a stronger nucleophile than water, yet cyanide requires presence of copper(I). It's probably not appropriate to call copper a catalyst, since it's present in stoichiometric amounts. $\endgroup$ – jerepierre Dec 15 '15 at 1:09
  • $\begingroup$ The copper is not always added in a stoichiometric amount. The reaction with just water requires an input of heat to effect the reaction. $\endgroup$ – A.K. Dec 15 '15 at 1:13
  • $\begingroup$ The answer says that oxygen must be oxidized by diazonium in order to avoid the need for copper. Is there evidence that water is oxidized in this reaction? $\endgroup$ – jerepierre Dec 15 '15 at 20:33

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.